CN103222082A - Organic electroluminescent element - Google Patents
Organic electroluminescent element Download PDFInfo
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- CN103222082A CN103222082A CN2011800563133A CN201180056313A CN103222082A CN 103222082 A CN103222082 A CN 103222082A CN 2011800563133 A CN2011800563133 A CN 2011800563133A CN 201180056313 A CN201180056313 A CN 201180056313A CN 103222082 A CN103222082 A CN 103222082A
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- 230000004888 barrier function Effects 0.000 claims abstract description 67
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 194
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 97
- 125000003118 aryl group Chemical group 0.000 claims description 92
- 125000001072 heteroaryl group Chemical group 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 53
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000001624 naphthyl group Chemical group 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 238000002347 injection Methods 0.000 abstract description 6
- 239000007924 injection Substances 0.000 abstract description 6
- -1 BPhen phenanthroline derivatives Chemical class 0.000 description 223
- 239000010410 layer Substances 0.000 description 216
- 239000002585 base Substances 0.000 description 192
- 150000001721 carbon Chemical group 0.000 description 96
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 39
- 239000000463 material Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 37
- 125000004429 atom Chemical group 0.000 description 31
- 230000005540 biological transmission Effects 0.000 description 29
- 125000000753 cycloalkyl group Chemical group 0.000 description 27
- 241001597008 Nomeidae Species 0.000 description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 23
- 239000002019 doping agent Substances 0.000 description 21
- 230000005855 radiation Effects 0.000 description 20
- 125000005605 benzo group Chemical group 0.000 description 19
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 19
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 16
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 15
- 230000005525 hole transport Effects 0.000 description 13
- 125000004104 aryloxy group Chemical group 0.000 description 12
- 230000007704 transition Effects 0.000 description 12
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 11
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 11
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 10
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 10
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 125000003710 aryl alkyl group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 125000005561 phenanthryl group Chemical group 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 125000001118 alkylidene group Chemical group 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 238000001296 phosphorescence spectrum Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000005281 excited state Effects 0.000 description 6
- 230000005283 ground state Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000002779 inactivation Effects 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- 150000001454 anthracenes Chemical class 0.000 description 5
- 230000001174 ascending effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000005956 isoquinolyl group Chemical group 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000004957 naphthylene group Chemical group 0.000 description 5
- 125000003373 pyrazinyl group Chemical group 0.000 description 5
- 125000005493 quinolyl group Chemical group 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000001769 aryl amino group Chemical group 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 4
- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 description 4
- 125000002541 furyl group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002790 naphthalenes Chemical class 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 4
- 229910052705 radium Inorganic materials 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 3
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical group C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 3
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000006278 bromobenzyl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000005299 dibenzofluorenyl group Chemical group C1(=CC=CC2=C3C(=C4C=5C=CC=CC5CC4=C21)C=CC=C3)* 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 125000006178 methyl benzyl group Chemical group 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000006502 nitrobenzyl group Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000005562 phenanthrylene group Chemical group 0.000 description 3
- 238000005539 phosphorimetry Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 125000001725 pyrenyl group Chemical group 0.000 description 3
- 125000002098 pyridazinyl group Chemical group 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 0 *N(*)*C=CBr Chemical compound *N(*)*C=CBr 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- MLNNTIDTRGJCAV-UHFFFAOYSA-N 4-(1,3-oxazol-2-yl)oxadiazole Chemical compound C1=COC(C=2N=NOC=2)=N1 MLNNTIDTRGJCAV-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
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- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 2
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 description 2
- TUAHORSUHVUKBD-UHFFFAOYSA-N benzo[c]phenanthrene Chemical group C1=CC=CC2=C3C4=CC=CC=C4C=CC3=CC=C21 TUAHORSUHVUKBD-UHFFFAOYSA-N 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000005945 imidazopyridyl group Chemical group 0.000 description 2
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000005054 naphthyridines Chemical class 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 150000002987 phenanthrenes Chemical class 0.000 description 2
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 2
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- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- LLAPDLPYIYKTGQ-UHFFFAOYSA-N 1-aminoethyl Chemical group C[CH]N LLAPDLPYIYKTGQ-UHFFFAOYSA-N 0.000 description 1
- 125000006083 1-bromoethyl group Chemical group 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003852 3-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(Cl)=C1[H])C([H])([H])* 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002219 fluoranthenes Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006504 o-cyanobenzyl group Chemical group [H]C1=C([H])C(C#N)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- VXPCQISYVPFYRK-UHFFFAOYSA-N profenamine hydrochloride Chemical compound Cl.C1=CC=C2N(CC(C)N(CC)CC)C3=CC=CC=C3SC2=C1 VXPCQISYVPFYRK-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
The invention provides an organic electroluminescent element, which comprises an anode, a luminescent layer, a barrier layer, an electron injection layer and a cathode in sequence, wherein the luminescent layer contains a main body and a styrylamine derivative with a specific structure, and the barrier layer has 3-state energy ET bEnergy E of 3-state of more than main bodyT hIs large.
Description
Technical field
The present invention relates to organic electroluminescent (EL) element, particularly high efficiency organic EL.
Background technology
If organic EL is classified according to its principle of luminosity, then can be divided into two kinds on fluorescent type and phosphorescence type.When organic EL is applied voltage, from the anode injected hole, and inject electronics from negative electrode, the two is compound and form exciton in luminescent layer.According to the statistical theory of electron spin, singlet state exciton and 3 heavy attitude excitons generate according to 25%: 75% ratio.Use luminous based on the singlet state exciton in the fluorescent type, therefore it is said that the limit of internal quantum is 25%.The long lifetime technology constantly develops in having used fluorescent materials type element recently, be used in gradually in the full color display such as mobile phone, TV, but its high efficiency becomes problem.
About the high efficiency technology of fluorescent type element, disclose several be not used effectively so far obtain luminous technology from 3 heavy attitude excitons.For example, to the anthracene based compound is resolved as the non-doping element of material of main part, with regard to its mechanism, bumping to merge by two 3 heavy attitude excitons generates the singlet state exciton in non-patent literature 1, and its result makes the fluorescence radiation increase.Yet, in non-patent literature 1, only disclose and in the non-doping element of material of main part is only arranged, confirm, and its effect is low because of 3 heavy attitude exciton collision and fusion cause fluorescence radiation to increase, only be 3～6% based on the efficient recruitment of 3 heavy attitude excitons.
Reported in the non-patent literature 2 that the internal quantum in blue fluorescent element is 28.5%, surpassed theoretical boundary 25% in the past.But, any technological means of 25% that is used for surpassing is not disclosed, in addition, the viewpoint from the practicability of the organic EL TV of full color requires further high efficiency.
In addition, other examples that utilize 3 heavy attitude excitons in fluorescent element are disclosed in the patent documentation 1.In common organic molecule, exist minimum 3 heavy attitude excited states (T1) lower than minimum singlet state excited state (S1), but higher 3 heavy attitude excited states (T2) situation higher than S1.In this case, by causing, can obtain luminous based on the singlet state excited state from the transition of T2 to S1.Yet in fact external quantum efficiency is about 6% (light is taken out efficient be made as 25% o'clock, internal quantum is 24%), does not surpass described limiting value 25% in the past.In addition, with regard to mechanism herein, depend in a part from the intersystem crossing (intersystem crossing) of 3 heavy attitude excited states to the singlet state excited state, do not cause non-patent literature 1 disclosed generation phenomenon by the singlet state due to the collision of two 3 heavy attitude excitons.
Disclose in the patent documentation 2,3 by in the hole blocking layer of fluorescent element, using BCP (bathocuproine (Bathocuproin)), BPhen phenanthroline derivatives such as (bathophenanthrolines) to improve the efficient compound technology of hole density, initiation at the interface of hole blocking layer and luminescent layer.Yet phenanthroline derivatives such as BCP (bathocuproine), BPhen are fragility to the hole, the oxidation poor durability, and from the viewpoint of the long lifetime of element, performance is insufficient.
In addition, the examples of material as the electron transfer layer that joins with luminescent layer such as the aromatic compound that uses anthracene derivant is disclosed in the patent documentation 4,5 in fluorescent element.Yet, in these examples, owing to the singlet state exciton that is generated is to be the element that prerequisite is designed to carry out fluorescence radiation in the short time, therefore need not to consider relation with the 3 heavy attitude energy that design the electron transfer layer in so-called phosphorescent element usually, in fact 3 of electron transfer layer heavy attitude energy are littler than 3 heavy attitude energy of luminescent layer, therefore the 3 heavy attitude excitons that generate in the luminescent layer can diffuse to electron transfer layer, experience the heat inactivation process subsequently, the theoretical boundary that is difficult to surpass fluorescence radiation in the past promptly 25%.And then because the affinity of electron transfer layer is excessive, so electronics is poor to the injection of the little luminescent layer of affinity, may not necessarily obtain the such effect of high efficiency.In addition, disclosing in the patent documentation 6 and having used the fluoranthene that shows long-life, high efficiency blue-light-emitting is the element of dopant, but it may not deserve to be called high efficiency.
On the other hand, the phosphorescence type directly uses based on 3 and weighs the luminous of attitude excitons.Because the singlet state exciton energy also can be converted into 3 heavy attitude excitons by the spin of light emitting molecule inside, therefore the expectation acquisition is in theory near 100% internal light emission efficiency.Therefore, comfortable 2000 by Forrest etc. delivered use the Ir complex compound and the phosphorescence light-emitting component since, as the high efficiency technology of organic EL, the phosphorescence light-emitting component enjoys to be gazed at.Yet though red phosphor elements has reached the stage of practicability, green, blue phosphorescent element is shorter than fluorescent type component life, and particularly blue phosphorescent exists short and colorimetric purity of life-span, the inadequate problem of luminous efficiency, and present situation is not reach practicability.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-214180 communique
Patent documentation 2: Japanese kokai publication hei 10-79297 communique
Patent documentation 3: TOHKEMY 2002-100478 communique
Patent documentation 4: TOHKEMY 2003-338377 communique
Patent documentation 5: international disclosing No. 2008/062773
Patent documentation 6: international disclosing No. 2007/100010
Patent documentation 7: Japanese Unexamined Patent Application Publication 2002-525808 communique
Patent documentation 8: No. 7018723 specification of United States Patent (USP)
Non-patent literature
Non-patent literature 1:Journal of Applied Physics, 102,114504 (2007)
Non-patent literature 2:SID2008 DIGEST, 709 (2008)
Summary of the invention
Therefore, the inventor etc. are conceived to non-patent literature 1 described certain phenomenon, promptly because of the collision and fusion of two 3 heavy attitude excitons generate the singlet state exciton phenomenon (below, be called Triplet-Triplet Fusion=TTF phenomenon), implement to cause the TTF phenomenon efficiently and realize the research of the high efficiency of fluorescent element.Particularly, use 3 heavy attitude energy than the big material of the main body that constitutes luminescent layers as with the layer (being called the barrier layer among the present invention) of the cathode side interface adjacency of luminescent layer the time, 3 heavy attitude excitons can be bound in the luminescent layer, cause the TTF phenomenon efficiently, thereby realize the high efficiency and the long-life of fluorescent element.
In addition, for prevent in phosphorescence type element exciton life-span than the long 3 heavy attitude excitons of singlet state exciton to the luminescent layer outdiffusion, known to using the big materials of 3 heavy attitude energy as realizing high efficiency scheme with the layer of the cathode side interface adjacency of luminescent layer.Disclose in the Japanese Unexamined Patent Application Publication 2002-525808 communique by coming bound hole, exciton in abutting connection with the ground setting by the barrier layer that the BCP (bathocuproine) as phenanthroline derivative forms, realized the technology of high efficiency thus with luminescent layer.In addition, in No. 7018723 specification of United States Patent (USP), put down in writing by in hole blocking layer, using specific aromatic ring compound to realize the scheme of high efficiency, long lifetime.Yet, for these documents, above-mentioned TTF phenomenon is called as TTA (Triplet-Triplet Annihiration:3 is heavy, and attitude is buried in oblivion) in phosphorescence type element, the feature that is acknowledged as infringement phosphorescence we can say that promptly based on the luminous phenomenon of 3 heavy attitude excitons the practice that as the present invention 3 heavy attitude excitons is strapped in the luminescent layer efficiently may not be associated with high efficiency in phosphorescence type element.
According to the present invention, provide following organic EL.
1. organic electroluminescent device, it possesses anode, luminescent layer, barrier layer, electron injecting layer and negative electrode successively,
Described luminescent layer contains main body and following formula (1) or (2) represented styrylamine derivative,
The 3 heavy attitude energy on described barrier layer are bigger than 3 heavy attitude energy of described main body.
(in the formula (1), Ar
1～Ar
4Be respectively replacement or the aryl of non-replacement or the heteroaryl of replacement or non-replacement,
Ar
5～Ar
7Be respectively replacement or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement,
L, m and n are respectively 1～3 integer, and p is 0～2 integer,
At l is 2 when above, Ar
5Can be identical or different respectively,
At m is 2 when above, Ar
6Can be identical or different respectively,
At p is more than 1 and n is 2 when above, Ar
7Can be identical or different respectively,
At p is more than 2 and n is 1 o'clock, Ar
7Can be identical or different respectively,
Ar
1～Ar
7Substituting group be the silicyl or the cyano group of halogen atom, alkyl, aryl, heteroaryl, alkoxyl, replacement or non-replacement,
Wherein, at p=0 and (Ar
5)
1During for biphenylene, (Ar
6)
mFor carbon number is a arlydene more than 7, at p=0 and (Ar
6)
mDuring for biphenylene, (Ar
5)
1For carbon number is a arlydene more than 7.)
(in the formula (2), Ar
8Be replacement or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement,
A
1And A
2Be respectively the heteroaryl or the represented group of following formula (3) of aryl, replacement or the non-replacement of alkyl, replacement or non-replacement,
(in the formula (3), Ar
9For replacing or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement B
2For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement, at A
1And A
2When being the group of formula (3), Ar
9And B
2Can be identical or different respectively.)
B
1For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement.
Ar
8～Ar
9, A
1, A
2, B
1And B
2Substituting group be the silicyl or the cyano group of halogen atom, alkyl, aryl, heteroaryl, alkoxyl, replacement or non-replacement.)
2. according to 1 described organic electroluminescent device, wherein, in described formula (1) or (2), Ar
1～Ar
4, A
1, A
2, B
1And B
2Has the substituting group that at least one is selected from the silicyl of cyano group, fluorine atom and replacement or non-replacement.
3. according to 1 or 2 described organic electroluminescent devices, wherein, in the described formula (1), p is 0, and l is 1, and m is 1.
4. according to 1 or 2 described organic electroluminescent devices, wherein, in the described formula (1), p is 1, and l is 1, and m is 1, and n is 1.
5. according to 1 or 2 described organic electroluminescent devices, wherein, in the described formula (1), p is 0, and l is 1, and m is 2.
6. according to 1 or 2 described organic electroluminescent devices, wherein, in the described formula (1), p is 0, and l is 2, and m is 2.
7. according to 1 or 2 described organic electroluminescent devices, wherein, in the described formula (1), p is 1, and l is 2, and m is 2, and n is 2.
8. according to 1 described organic electroluminescent device, wherein, in the described formula (1), Ar
5～Ar
7In at least one for replacing or the naphthyl of fluorenyl, replacement or the non-replacement of non-replacement or the phenyl of replacement or non-replacement.
9. according to 1 described organic electroluminescent device, wherein, in the described formula (2), Ar
8And Ar
9In at least one for replacing or the naphthyl of fluorenyl, replacement or the non-replacement of non-replacement or the phenyl of replacement or non-replacement.
10. according to each described organic electroluminescent device in 1～8, wherein, in the described formula (1), the structure between two nitrogen is any in the following formula.
(in various, the wave at two ends is connected on the nitrogen-atoms.)
According to the present invention, cause the TTF phenomenon efficiently in luminescent layer inside, high efficiency organic EL can be provided.
Description of drawings
Fig. 1 is the figure of an example of the organic EL of expression the 1st execution mode.
Fig. 2 A is the figure of relation of the energy bandgaps of expression each layer of the present invention.
Fig. 2 B is the figure of expression based on the effect of the relation of the energy bandgaps of each layer of the present invention.
Fig. 3 is the figure of the assay method of expression transition EL waveform.
Fig. 4 is the figure of expression from the assay method of the luminous strength ratio of TTF.
Fig. 5 is the figure of an example of the organic EL of expression the 2nd execution mode.
Fig. 6 is the figure of an example of the organic EL of expression the 3rd execution mode.
Fig. 7 is the figure of an example of the organic EL of expression the 4th execution mode.
Embodiment
＜the 1 execution mode 〉
The present invention is a technology of utilizing the TTF phenomenon.The TTF phenomenon at first, below is described.
From anode, negative electrode injected holes, electronics, compound and generate exciton in luminescent layer.For its spin states, known in the past, the singlet state exciton is 25% ratio, and 3 heavy attitude excitons are 75% ratio.In known in the past fluorescent element, 25% singlet state exciton relaxation is luminous during to ground state, and remaining 75% 3 heavy attitude excitons are not luminous and experience heat inactivation process is returned ground state.Therefore, the theoretical boundary of the internal quantum of fluorescent element in the past is called as 25%.
On the other hand, theoretical research is carried out in the 3 heavy attitude exciton behaviors that generate for organic substance inside.According to the viewpoint (J.Phys.Cem.A, 104,7711 (2000)) of S.M.Bachilo etc., can get back to 3 heavy attitudes rapidly if suppose the exciton of high levels such as 5 heavy attitudes, then 3 heavy attitude excitons (below, be designated as
3A
*) density when rising, 3 heavy attitude excitons bump each other, cause the reaction of following formula.Here,
1A represents ground state,
1A
*Expression lowest excited singlet state exciton.
3A
*+
3A
*→(4/9)
1A+(1/9)
1A
*+(13/9)
3A
*
That is, 5
3A
*→ 4
1A+
1A
*, estimate that 1/5 promptly 20% is changed to the singlet state exciton in initial 75% the 3 heavy attitude excitons that generate.Therefore, for producing the helpful singlet state exciton of light, in initial 25% the amount that generates, increase by 75% * (1/5)=15%, become 40%.At this moment, be 15/40 from the luminous ratio of TTF shared ratio (TTF ratio) in total luminous intensity, promptly 37.5%.In addition, when 75% 3 heavy attitude excitons of initial generation run foul of each other and when generating singlet state exciton (generating 1 singlet state exciton by two 3 heavy attitude excitons), in 25% amount of the initial singlet state exciton that generates, increase by 75% * (1/2)=37.5%, can obtain 62.5% this very high internal quantum.At this moment, the TTF ratio becomes 37.5/62.5=60%.
Fig. 1 is the summary pie graph of organic EL of an example of expression the 1st execution mode of the present invention.Fig. 2 A schematically shows the lowest excited singlet state energy level and the lowest excited triplet energy level of each layer.Need to prove, among the present invention, triplet energies is meant the poor of energy under the lowest excited triplet state and the energy under the ground state, and singlet state energy (being also referred to as energy bandgaps sometimes) is meant the poor of energy under the lowest excited singlet state state and the energy under the ground state.Organic EL shown in Figure 1 stacks gradually hole transport zone 50, luminescent layer 20, electric transmission zone 30 and negative electrode 40 from anode 10.Preferably between anode 10 and luminescent layer 20, hole transport zone 50 is set.In addition, among the present invention, when only being called the barrier layer, be meant the layer that has barrier functionality for triplet energies.Therefore, hole blocking layer is meant the layer that this function is different with electric charge barrier layer.
Among Fig. 2 A, inject to luminescent layer via the hole transport zone, inject to luminescent layer via the electric transmission zone from the negative electrode injected electrons from the anode injected holes.Subsequently, hole and electron recombination in luminescent layer generate singlet state exciton and triplet exciton.Both of these case is taking place and is taking place in compound being divided on dopant molecule on the host molecule.Among Fig. 2 A, the triplet energies of hole transport zone, main body, dopant is made as E respectively
T H0, E
T h, E
T d, the singlet state energy of main body, dopant is made as E respectively
S h, E
S d
Among the present invention, the electric transmission zone has the barrier layer in the part with the luminescent layer adjacency.The barrier layer, is strapped in 3 heavy attitude excitons in the luminescent layer to the diffusion of electric transmission zone by the 3 heavy attitude excitons that prevent to generate at luminescent layer, thereby improves the density of 3 heavy attitude excitons, has the function of efficient initiation TTF phenomenon.In order to prevent 3 heavy attitude exciton diffusions, preferably make the 3 heavy attitude ENERGY E on barrier layer
T bCompare E
T hGreatly and compare E
T dAlso big.The barrier layer prevents 3 heavy attitude excitons to the diffusion of electric transmission zone, and therefore 3 of main body heavy attitude excitons become the singlet state exciton efficiently in luminescent layer, and its singlet state exciton moves on dopant, makes the optical energy inactivation.
As the material that forms the barrier layer, preferably select hydrocarbon aromatic ring compound.More preferably select polycyclc aromatic compound.Therefore these materials are difficult to deterioration owing to have anti-hole property, and the life-span is elongated.
Fig. 2 B represents particularly preferred execution mode.Main body and dopant preferably satisfy E
T h＜E
T dRelation.By satisfying this relation, like that, compound and the triplet exciton that produces can not move to the dopant with higher triplet energies on main body shown in Fig. 2 B.In addition, compound and the triplet exciton that produces shifts energy to host molecule rapidly on dopant molecule.That is, the triplet exciton of main body can not move to dopant, bumps on main body efficiently each other based on TTF phenomenon triplet exciton, generates the singlet state exciton thus.And then, because the singlet state ENERGY E of dopant
S dSinglet state ENERGY E than main body
S hLittle, therefore the singlet state exciton that generates based on the TTF phenomenon shifts energy from main body to dopant, helps the fluorescence of dopant luminous.At the dopant that is used for the fluorescent type element, forbade originally from the excited triplet state state that to ground state transition, triplet exciton the optical energy inactivation did not take place and causes heat inactivation in such transition.But the pass of the triplet energies by making main body and dopant is an above-mentioned relation, thereby triplet exciton generates the singlet state exciton efficiently in that the mutual collision of heat inactivation cause takes place, and makes luminous efficiency improve.
In the electric transmission zone, the electron injecting layer that injects electronics easily from negative electrode is set between barrier layer and negative electrode.As concrete example, can use the electron injecting layer that common electric transmission material and alkali metal compound, alkali metal or alkali metal complex are laminated; Perhaps adding with alkali metal compound, alkali metal or alkali metal complex in forming the material on barrier layer is the electron injecting layer that the donor of representative forms.
Luminescent layer of the present invention contains main body and specific styrylamine derivative.Spendable styrylamine derivative is represented with following formula (1) among the present invention.
In the formula (1), Ar
1～Ar
4Be respectively and replace or the aryl (preferably making into the ring carbon atom number is 6～20) of non-replacement or the heteroaryl (preferably making into the annular atoms number is 5～20) of replacement or non-replacement.Preferably make Ar
1～Ar
4The one-tenth ring carbon atom number that is respectively replacement or non-replacement is 6～20 aryl, more preferably makes Ar
1～Ar
4Be respectively phenyl, the naphthyl of replacement or non-replacement.
Ar
5～Ar
7Be respectively and replace or the arlydene (preferably making into the ring carbon atom number is 6～20) of non-replacement or the inferior heteroaryl (preferably making into the annular atoms number is 5～20) of replacement or non-replacement.Preferably make Ar
5～Ar
7The one-tenth ring carbon atom number that is respectively replacement or non-replacement is 6～20 arlydene, more preferably makes Ar
5～Ar
7Be respectively and replace or the fluorenylidene of naphthylene, replacement or the non-replacement of phenylene, replacement or the non-replacement of non-replacement or the phenanthrylene of replacement or non-replacement.Ar
5～Ar
7In at least 1 for replacing or the fluorenylidene of naphthylene, replacement or the non-replacement of phenylene, replacement or the non-replacement of non-replacement or the phenanthrylene of replacement or non-replacement.Substituting group preferred alkyl (preferably making carbon number is 1～6, more preferably 1～4).
L, m and n are respectively 1～3 integer, are preferably 1.At l is 2 when above, Ar
5Can be identical or different respectively, be 2 when above at m, Ar
6Can be identical or different respectively, be more than 1 and n is 2 when above, Ar at p
7Can be identical or different respectively, be more than 2 and n is 1 o'clock, Ar at p
7Can be identical or different respectively.
P is 0～2 integer, is preferably 0～1 integer, more preferably 0 this integer.At p is 0 o'clock, becomes singly-bound.
Above-mentioned aryl, arlydene, heteroaryl, inferior heteroaryl can be the groups that comprises the ring more than 1, also can be the groups that a plurality of rings condense.
So-called " one-tenth ring carbon atom " is meant the carbon atom that constitutes saturated rings, unsaturated ring or aromatic rings, and so-called " one-tenth annular atoms " is meant carbon atom and the hetero-atom that constitutes heterocycle (comprising saturated rings, unsaturated ring and aromatic rings).
Ar
1～Ar
4One-tenth ring carbon atom number be 6～20 aryl, be preferably into the ring carbon atom number and be 6～12 aryl.
As the concrete example of aryl, can enumerate phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, aphthacene base, pyrenyl,
Base, benzo [c] phenanthryl, benzo [g]
Base, benzo [9,10] phenanthryl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-fluorenyl, benzo fluorenyl, dibenzo fluorenyl, 2-xenyl, 3-xenyl, 4-xenyl, terphenyl, fluoranthene base etc. are preferably phenyl, biphenyl, tolyl, xylyl, 1-naphthyl.
Ar
1～Ar
4One-tenth annular atoms number be that to be preferably into the annular atoms number be 5～14 heteroaryl for 5～20 heteroaryl.
Concrete example as heteroaryl, can enumerate pyrrole radicals, pyrazinyl, pyridine radicals, indyl, isoindolyl, imidazole radicals, furyl, benzofuranyl, isobenzofuran-base, the 1-dibenzofuran group, the 2-dibenzofuran group, the 3-dibenzofuran group, the 4-dibenzofuran group, 1-dibenzothiophenes base, 2-dibenzothiophenes base, 3-dibenzothiophenes base, 4-dibenzothiophenes base, quinolyl, isoquinolyl, quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, phenanthridinyl, acridinyl, the phenanthroline base, phenazinyl, phenothiazinyl phenoxazine group oxazolyl oxadiazole base, the furazan base, thienyl, benzothienyl etc., preferred 1-dibenzofuran group, the 2-dibenzofuran group, the 3-dibenzofuran group, the 4-dibenzofuran group, 1-dibenzothiophenes base, 2-dibenzothiophenes base, 3-dibenzothiophenes base, 4-dibenzothiophenes base, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl.
As Ar
5, Ar
6And Ar
7One-tenth ring carbon atom number be that the arlydene of 6～20 (preferred 6～12) is the concrete example of the inferior heteroaryl of 5～20 (preferred 5～14) with becoming the annular atoms number, can enumerate and above-mentioned Ar
1～Ar
4One-tenth ring carbon atom number be 6～20 aryl with becoming the annular atoms number be the divalent group of the concrete example correspondence of 5～20 heteroaryl.Can preferably enumerate divalent groups such as phenyl, fluorenyl, naphthyl, phenanthryl, xenyl, dibenzo fluorenyl, pyridine radicals, isoquinolyl.
In addition, as Ar
5, Ar
6And Ar
7Replacement or the arlydene of non-replacement, can following group be shown example.
In the formula, Y
1, Y
2, X
1～X
8Aryl or replacement silicyl for hydrogen atom, alkyl, cycloalkyl, replacement or non-replacement.In addition, X
1With X
2, X
2With X
3, X
3With X
4, X
5With X
6, X
6With X
7, X
7With X
8Can interosculate respectively and form following illustrated saturated or undersaturated circulus.Above-mentioned circulus can also have substituting group.Wherein, when forming circulus, from X
1～X
8Select with the binding site of circulus any two, can connect with the singly-bound form.
(in various, the wave at two ends is connected on the nitrogen-atoms)
Above-mentioned Ar
1～Ar
7Substituting group be the silicyl or the cyano group of halogen atom, alkyl, aryl, heteroaryl, alkoxyl, replacement or non-replacement, be preferably and replace or silicyl, cyano group, the fluorine atom of non-replacement.
As alkyl, can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl etc.
The carbon number of abovementioned alkyl is for being preferably 1～10, and more preferably 1～6.Especially be preferably methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl.
Alkoxyl is represented with-OY, as the example of Y, can be enumerated the example of abovementioned alkyl.Alkoxyl for example is methoxyl group, ethyoxyl.
Replacing silicyl comprises and replacing or the carbon number of non-replacement is that the carbon number of 1～20 alkyl silicyl (comprising monoalkyl silicyl, dialkyl group silicyl and trialkylsilkl) and replacement or non-replacement is 6～30 aryl silicyl (comprising dialkyl aryl silicyl, alkyl diaryl silicyl and diarye silyl).
Above-mentioned carbon number be 1～20 alkyl silicyl to be preferably carbon number be 1～10 alkyl silicyl, more preferably carbon number is 1～6 alkyl silicyl.As the concrete example of alkyl silicyl, can enumerate trimethyl silyl, triethylsilyl, t-butyldimethylsilyl, vinyl-dimethyl base silicyl, propyl-dimethyl silicyl etc.
Above-mentioned carbon number be 6～30 aryl silicyl to be preferably carbon number be 6～20 aryl silicyl, more preferably carbon number is 6～10 aryl silicyl.As the concrete example of aryl silicyl, can enumerate triphenyl silicyl, phenyl dimetylsilyl, t-butyldiphenylsilyl, trimethylphenyl silicyl, three (xylyl) silicyl, three naphthyl silicyls etc.
As halogen atom, can enumerate fluorine, chlorine, bromine, iodine etc., preferred fluorine atom.
Below, example illustrates the structure between two nitrogen in the above-mentioned formula (1).
(in various, the wave at two ends is connected on the nitrogen-atoms)
Below, the concrete example of the compound of formula (1) is shown.
In addition, spendable styrylamine derivative is represented with following formula (2) among the present invention.
In the formula (2), Ar
8For replacing or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement.
A
1And A
2Be respectively the heteroaryl or the represented group of following formula (3) of aryl, replacement or the non-replacement of alkyl, replacement or non-replacement.
(in the formula (3), Ar
9For replacing or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement B
2For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement A
1And A
2When being the group of formula (3), Ar
9And B
2Can be identical or different respectively.)
B
1For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement.
Preferably make Ar
8～Ar
9In more than at least 1 for replacing or the naphthylene of non-replacement or the fluorenylidene of replacement or non-replacement.
As A
1And A
2Alkyl, (preferred carbon number is 1～8 for carbon number is 1～10, more preferably carbon number is 1～6) alkyl, as concrete example, can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl etc.
As A
1, A
2, B
1, B
2Replacement or the aryl of non-replacement, for becoming the ring carbon atom number is that 6～30 (being preferably the ring carbon atom number is 6～20, more preferably becoming the ring carbon atom number is 6～12) replacement or the aryl of non-replacement, as concrete example, can enumerate replace or the phenyl of non-replacement, naphthyl, anthryl, phenanthryl, aphthacene base, anthryl,
Base, fluorenyl, benzo [9,10] phenanthryl, pyrenyl, xenyl, para-terpheny base, meta-terphenyl base, o-tolyl, a tolyl, p-methylphenyl, to tert-butyl-phenyl, to (phenyl propyl) phenyl, methyl naphthyl, methyl anthryl, methyl biphenyl, tert-butyl group para-terpheny base, dimethyl fluorenyl, an xenyl, adjacent xenyl, 4-(2-phenyl-propane-2-yl) phenyl, fluoranthene base, 9,9 '-dimethyl fluorenyl, benzo-9,9 '-dimethyl fluorenyl, dibenzo-9,9 '-dimethyl fluorenyl etc.In addition, can be the aromatic series base (for example, phenyl napthyl, naphthyl phenyl, naphthyl naphthyl, naphthyl naphthyl naphthyl, phenyl naphthyl, naphthyl naphthyl phenyl, naphthyl phenyl napthyl, naphthyl phenyl, phenyl napthyl naphthyl, phenyl napthyl phenyl etc.) that phenyl, phenylene, naphthyl, naphthylene are combined.
Can preferably enumerate replace or the phenyl of non-replacement, xenyl, terphenyl, naphthyl, phenanthryl, anthryl,
Aromatic series bases such as base, fluorenyl.
Especially preferably make A
1, A
2, B
1, B
2Be respectively phenyl, xenyl, naphthyl, the fluorenyl of replacement or non-replacement.
As A
1, A
2, B
1, B
2Replacement or the heteroaryl of non-replacement, for becoming the annular atoms number is that 5～30 (being preferably the annular atoms number is 5～20, more preferably becoming the annular atoms number is 5～12) replacement or the heteroaryl of non-replacement, as concrete example, can enumerate the pyrrole radicals of replacement or non-replacement, pyrazinyl, pyridine radicals, indyl, isoindolyl, furyl, benzofuranyl, dibenzofuran group, isobenzofuran-base, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthridinyl, acridinyl, the phenanthroline base, phenazinyl, phenothiazinyl phenoxazine group oxazolyl oxadiazole base, the furazan base, thienyl, the methylpyrrole base, tert-butyl group pyrrole radicals, (phenyl propyl) pyrrole radicals, the methyl indol base, tert-butyl group indyl, the dibenzothiophenes base, pyrimidine radicals, pyridazinyl etc.
Can preferably enumerate dibenzofuran group, pyridine radicals and the carbazyl of replacement or non-replacement.
Especially preferably make A
1And A
2Be respectively the dibenzofuran group of replacement or non-replacement.
As Ar
8And Ar
9Replacement or the arlydene of non-replacement, can enumerate A
1, A
2, B
1, B
2Replacement or the divalent group of the aryl of non-replacement.
Phenylene, biphenylene, inferior terphenyl, naphthylene, phenanthrylene, anthrylene, the Asia of preferred replacement or non-replacement
Aromatic series bases such as base, fluorenylidene, inferior benzo [9,10] phenanthryl.
In addition, as Ar
8And Ar
9Replacement or the arlydene of non-replacement, can following group be shown example.
In the formula, Y
1, Y
2, X
1～X
8Aryl or replacement silicyl for hydrogen atom, alkyl, cycloalkyl, replacement or non-replacement.X
1With X
2, X
2With X
3, X
3With X
4, X
5With X
6, X
6With X
7, X
7With X
8Can interosculate respectively and form following illustrated saturated or undersaturated circulus.Above-mentioned circulus can also have substituting group.Wherein, when forming circulus, from X
1～X
8Select with the binding site of circulus any two, can connect with the singly-bound form.
(in various, the wave at two ends is connected on the nitrogen-atoms)
As Ar
8And Ar
9Replacement or the inferior heteroaryl of non-replacement, can enumerate A
1, A
2, B
1, B
2Replacement or the divalent group of the heteroaryl of non-replacement.
The preferred replacement or the inferior dibenzofuran group of non-replacement, inferior pyridine radicals and inferior carbazyl.
Ar
8, Ar
9, A
1, A
2, B
1, B
2Substituting group and Ar
1～Ar
7Identical.
Below, the concrete example of the compound of formula (2) is shown.
As main body, the represented anthracene derivant of preferred following formula (10).
In the formula (10), Ar
11And Ar
12Respectively independently for replacing or the one-tenth ring carbon atom number of non-replacement is 6～50 a aryl or to become the annular atoms number be 5～50 heterocyclic radical,
R
1～R
8Respectively independently for being selected from hydrogen atom, the one-tenth ring carbon atom number of replacement or non-replacement is 6～50 aryl, the one-tenth annular atoms number of replacement or non-replacement is 5～50 heterocyclic radical, the carbon number of replacement or non-replacement is 1～50 alkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 3～50 cycloalkyl, the carbon number of replacement or non-replacement is 1～50 alkoxyl, the carbon number of replacement or non-replacement is 7～50 aralkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～50 aryloxy group, the one-tenth ring carbon atom number of replacement or non-replacement is 6～50 arylthio, the carbon number of replacement or non-replacement is 2～50 alkoxy carbonyl, the silicyl of replacement or non-replacement, carboxyl, halogen atom, cyano group, group in nitro and the hydroxyl.
The preferred following anthracene derivant of anthracene derivant of the present invention (A), (B) and (C) in any, select according to the formation of the organic EL of using, the characteristic of needs.
(anthracene derivant (A))
For this anthracene derivant, the Ar in the formula (10)
11And Ar
12The one-tenth ring carbon atom number that is replacement or non-replacement respectively independently is 10～50 fused-aryl.As this anthracene derivant, can be divided into Ar
11And Ar
12Situation and Ar for the fused-aryl of identical replacement or non-replacement
11And Ar
12Situation for the fused-aryl of different replacements or non-replacement.
Particularly, can enumerate Ar in represented anthracene derivant of following formula (2-1)～(2-3) and the formula (10)
11And Ar
12Anthracene derivant for the fused-aryl of different replacements or non-replacement.
For the represented anthracene derivant of following formula (2-1), Ar
11And Ar
129-phenanthryl for replacement or non-replacement.
(in the formula (2-1), R
1～R
8It is same as described above,
R
11Be to be selected from hydrogen atom, the one-tenth ring carbon atom number of replacement or non-replacement is 6～50 aryl, the one-tenth annular atoms number of replacement or non-replacement is 5～50 heterocyclic radical, the carbon number of replacement or non-replacement is 1～50 alkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 3～50 cycloalkyl, the carbon number of replacement or non-replacement is 1～50 alkoxyl, the carbon number of replacement or non-replacement is 7～50 aralkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～50 aryloxy group, the one-tenth ring carbon atom number of replacement or non-replacement is 6～50 arylthio, the carbon number of replacement or non-replacement is 2～50 alkoxy carbonyl, the silicyl of replacement or non-replacement, carboxyl, halogen atom, cyano group, group in nitro and the hydroxyl
A is 0～9 integer.When a is integer more than 2, make two replace or condition that the phenanthryl of non-replacement is identical under, a plurality of R of existence
11Can be identical or different respectively.)
For the represented anthracene derivant of following formula (2-2), the Ar in the formula (10)
11And Ar
122-naphthyl for replacement or non-replacement.
(in the formula (2-2), R
1～R
8And R
11It is same as described above,
B is 1～7 integer.When b is integer more than 2, make two replace or condition that the 2-naphthyl of non-replacement is identical under, a plurality of R of existence
11Can be identical or different respectively.)
For the represented anthracene derivant of following formula (2-3), the Ar in the formula (10)
11And Ar
121-naphthyl for replacement or non-replacement.
(in the formula (2-3), R
1～R
8, R
11Same as described above with b.In addition, when b is integer more than 2, make two replace or condition that the 1-naphthyl of non-replacement is identical under, a plurality of R of existence
11Can be identical or different respectively.)
As the Ar in the formula (10)
11And Ar
12Anthracene derivant for the fused-aryl of different replacements or non-replacement preferably makes Ar
11And Ar
12For replace or the 2-naphthyl of 1-naphthyl, replacement or the non-replacement of 9-phenanthryl, replacement or the non-replacement of non-replacement in any.
Particularly, there is Ar
11Be 1-naphthyl and Ar
12Situation for the 2-naphthyl; Ar
11Be 1-naphthyl and Ar
12Situation for the 9-phenanthryl; And Ar
11Be 2-naphthyl and Ar
12Situation for the 9-phenanthryl.
(anthracene derivant (B))
For this anthracene derivant, the Ar in the formula (10)
11And Ar
12In one for replacing or the phenyl of non-replacement, another is for replacing or one-tenth ring carbon atom number of non-replacement is 10～50 fused-aryl.As this anthracene derivant, particularly, can enumerate following formula (2-4) and (2-5) represented anthracene derivant.
For the represented anthracene derivant of following formula (2-4), the Ar in the formula (10)
11Be the 1-naphthyl of replacement or non-replacement, Ar
12Phenyl for replacement or non-replacement.
(in the formula (2-4), R
1～R
8, R
11It is same as described above with b,
Ar
6For replacing or the one-tenth ring carbon atom number of non-replacement is 6～50 aryl, the carbon number of replacement or non-replacement is 1～50 alkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 3～50 cycloalkyl, the carbon number of replacement or non-replacement is 7～50 aralkyl, the one-tenth annular atoms number of replacement or non-replacement is 5～50 heterocyclic radical, 9,9-dimethyl fluorene-1-base, 9,9-dimethyl fluorene-2-base, 9,9-dimethyl fluorene-3-base, 9,9-dimethyl fluorene-4-base, dibenzofurans-1-base, dibenzofurans-2-base, dibenzofurans-3-base, perhaps dibenzofurans-4-base.In addition, Ar
6Also can form the ring of replacement or the fluorenyl of non-replacement or the dibenzofuran group of replacement or non-replacement etc. with the phenyl ring of its bonding.When b is integer more than 2, a plurality of R of existence
11Can be identical or different respectively.)
For the represented anthracene derivant of following formula (2-5), the Ar in the formula (10)
11Be the 2-naphthyl of replacement or non-replacement, Ar
12Phenyl for replacement or non-replacement.
(in the formula (2-5), R
1～R
8, R
11It is same as described above with b,
Ar
7For replacing or the one-tenth ring carbon atom number of non-replacement is that the one-tenth annular atoms number of 6～50 aryl, replacement or non-replacement is that the carbon number of 5～50 heterocyclic radical, replacement or non-replacement is that the one-tenth ring carbon atom number of 1～50 alkyl, replacement or non-replacement is that the carbon number of 3～50 cycloalkyl, replacement or non-replacement is 7～50 aralkyl, dibenzofurans-1-base, dibenzofurans-2-base, dibenzofurans-3-base or dibenzofurans-4-base.In addition, Ar
7Also can form the ring of replacement or the fluorenyl of non-replacement or the dibenzofuran group of replacement or non-replacement etc. with the phenyl ring of its bonding.When b is integer more than 2, a plurality of R of existence
11Can be identical or different respectively.)
(anthracene derivant (C))
This anthracene derivant represents with following formula (2-6), particularly, be preferably following formula (2-6-1), (2-6-2) and (2-6-3) in the represented derivative of any one formula.
(in the formula (2-6), R
1～R
8And Ar
6It is same as described above,
Ar
5For replacing or the one-tenth ring carbon atom number of non-replacement is that the carbon number of 6～50 aryl, replacement or non-replacement is that the one-tenth ring carbon atom number of 1～50 alkyl, replacement or non-replacement is that the carbon number of 3～50 cycloalkyl, replacement or non-replacement is that the one-tenth annular atoms number of 7～50 aralkyl or replacement or non-replacement is 5～50 heterocyclic radical, Ar
5And Ar
6Can select independently respectively.)
(in the formula (2-6-1), R
1～R
8Same as described above.)
(in the formula (2-6-2), R
1～R
8Same as described above.Ar
8For replacing or the one-tenth ring carbon atom number of non-replacement is 10～20 fused-aryl.)
(in the formula (2-6-3), R
1～R
8With used identical in the formula (10).
Ar
5aAnd Ar
6aThe one-tenth ring carbon atom number that is replacement or non-replacement respectively independently is 10～20 fused-aryl.)
As R
1～R
8, R
11, Ar
5～Ar
7, Ar
11And Ar
12The replacement or the one-tenth ring carbon atom number of non-replacement be 6～50 aryl, can enumerate phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 6-
Base, 1-benzo [c] phenanthryl, 2-benzo [c] phenanthryl, 3-benzo [c] phenanthryl, 4-benzo [c] phenanthryl, 5-benzo [c] phenanthryl, 6-benzo [c] phenanthryl, 1-benzo [g]
Base, 2-benzo [g]
Base, 3-benzo [g]
Base, 4-benzo [g]
Base, 5-benzo [g]
Base, 6-benzo [g]
Base, 7-benzo [g]
Base, 8-benzo [g]
Base, 9-benzo [g]
Base, 10-benzo [g]
Base, 11-benzo [g]
Base, 12-benzo [g]
Base, 13-benzo [g]
Base, 14-benzo [g]
Base, 1-triphenyl, 2-triphenyl, 2-fluorenyl, 9,9-dimethyl fluorene-2-base, benzo fluorenyl, dibenzo fluorenyl, 2-xenyl, 3-xenyl, 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, a tolyl, p-methylphenyl, to tert-butyl-phenyl, to (2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl, 4 "-tert-butyl group para-terpheny base-4-base etc.The one-tenth ring carbon atom number of the phenyl of preferred non-replacement, substituted-phenyl, replacement or non-replacement is the fluorenyl (2-fluorenyl) of 10～14 aryl (for example 1-naphthyl, 2-naphthyl, 9-phenanthryl), replacement or non-replacement and the pyrenyl (1-pyrenyl, 2-pyrenyl, 4-pyrenyl) of replacement or non-replacement.
In addition, as Ar
5a, Ar
6aAnd Ar
8The replacement or the one-tenth ring carbon atom number of non-replacement be 10～20 fused-aryl, can enumerate 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-fluorenyl etc.Preferred especially 1-naphthyl, 2-naphthyl, 9-phenanthryl and fluorenyl (2-fluorenyl).
As R
1～R
8, R
11, Ar
5～Ar
7, Ar
11And Ar
12The replacement or the one-tenth annular atoms number of non-replacement be 5～50 heterocyclic radical, can enumerate the 1-pyrrole radicals, the 2-pyrrole radicals, the 3-pyrrole radicals, pyrazinyl, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 2-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 1-dibenzofuran group, the 2-dibenzofuran group, the 3-dibenzofuran group, the 4-dibenzofuran group, 1-dibenzothiophenes base, 2-dibenzothiophenes base, 3-dibenzothiophenes base, 4-dibenzothiophenes base, quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1,7-phenanthroline-2-base, 1,7-phenanthroline-3-base, 1,7-phenanthroline-4-base, 1,7-phenanthroline-5-base, 1,7-phenanthroline-6-base, 1,7-phenanthroline-8-base, 1,7-phenanthroline-9-base, 1,7-phenanthroline-10-base, 1,8-phenanthroline-2-base, 1,8-phenanthroline-3-base, 1,8-phenanthroline-4-base, 1,8-phenanthroline-5-base, 1,8-phenanthroline-6-base, 1,8-phenanthroline-7-base, 1,8-phenanthroline-9-base, 1,8-phenanthroline-10-base, 1,9-phenanthroline-2-base, 1,9-phenanthroline-3-base, 1,9-phenanthroline-4-base, 1,9-phenanthroline-5-base, 1,9-phenanthroline-6-base, 1,9-phenanthroline-7-base, 1,9-phenanthroline-8-base, 1,9-phenanthroline-10-base, 1,10-phenanthroline-2-base, 1,10-phenanthroline-3-base, 1,10-phenanthroline-4-base, 1,10-phenanthroline-5-base, 2,9-phenanthroline-1-base, 2,9-phenanthroline-3-base, 2,9-phenanthroline-4-base, 2,9-phenanthroline-5-base, 2,9-phenanthroline-6-base, 2,9-phenanthroline-7-base, 2,9-phenanthroline-8-base, 2,9-phenanthroline-10-base, 2,8-phenanthroline-1-base, 2,8-phenanthroline-3-base, 2,8-phenanthroline-4-base, 2,8-phenanthroline-5-base, 2,8-phenanthroline-6-base, 2,8-phenanthroline-7-base, 2,8-phenanthroline-9-base, 2,8-phenanthroline-10-base, 2,7-phenanthroline-1-base, 2,7-phenanthroline-3-base, 2,7-phenanthroline-4-base, 2,7-phenanthroline-5-base, 2,7-phenanthroline-6-base, 2,7-phenanthroline-8-base, 2,7-phenanthroline-9-base, 2,7-phenanthroline-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 10-phenoxazine group, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base, the 2-thienyl, the 3-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl, the 4-tert-butyl group-3-indyl etc.Be preferably 1-dibenzofuran group, 2-dibenzofuran group, 3-dibenzofuran group, 4-dibenzofuran group, 1-dibenzothiophenes base, 2-dibenzothiophenes base, 3-dibenzothiophenes base, 4-dibenzothiophenes base, 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl, 9-carbazyl.
As R
1～R
8, R
11And Ar
5～Ar
7The replacement or the carbon number of non-replacement be 1～50 alkyl, can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxymethyl, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl group, 1, the 2-dihydroxy ethyl, 1,3-dihydroxy isopropyl, 2, the 3-dihydroxy tert-butyl group, 1,2,3-trihydroxy propyl group, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl group, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-dichloro tert-butyl group, 1,2,3-three chloropropyls, bromomethyl, the 1-bromoethyl, the 2-bromoethyl, 2-bromine isobutyl group, 1,2-two bromoethyls, 1,3-dibromo isopropyl, 2, the 3-dibromo tert-butyl group, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl group, 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-diiodo-tert-butyl group, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diaminourea isopropyl, 2, the 3-diaminourea tert-butyl group, 1,2,3-triamido propyl group, cyano methyl, the 1-cyano ethyl, the 2-cyano ethyl, 2-cyano group isobutyl group, 1,2-dicyano ethyl, 1,3-dicyano isopropyl, 2, the 3-dicyano tert-butyl group, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl group, 1,2-dinitro ethyl, 1,3-dinitro isopropyl, 2, the 3-dinitro tert-butyl group, 1,2,3-trinitro-propyl group etc.Be preferably methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group.
As R
1～R
8, R
11And Ar
5～Ar
7The substituent replacement or the one-tenth ring carbon atom number of non-replacement be 3～50 cycloalkyl, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 4-methylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norborny, 2-norborny etc.Preferred cyclopenta, cyclohexyl.
R
1～R
8And R
11The replacement or the carbon number of non-replacement be 1～50 alkoxyl for-group that OZ represents, Z is from above-mentioned R
1～R
8The replacement or the carbon number of non-replacement be to select in 1～50 the alkyl.
As R
1～R
8, R
11And Ar
5～Ar
7Substituent replacement or the carbon number of non-replacement be that (carbon number of aryl moiety is 6～49 to 7～50 aralkyl, the carbon number of moieties is 1～44), can enumerate benzyl, the 1-phenylethyl, the 2-phenylethyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, the phenyl tert-butyl group, the Alpha-Naphthyl methyl, 1-Alpha-Naphthyl ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl isopropyl, 2-Alpha-Naphthyl isopropyl, the betanaphthyl methyl, 1-betanaphthyl ethyl, 2-betanaphthyl ethyl, 1-betanaphthyl isopropyl, 2-betanaphthyl isopropyl, 1-pyrrole radicals methyl, 2-(1-pyrrole radicals) ethyl, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, adjacent iodine benzyl, to hydroxybenzyl, between hydroxybenzyl, adjacent hydroxybenzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-hydroxyl-2-propyloxy phenyl base, 1-chloro-2-propyloxy phenyl base etc.
R
1～R
8And R
11Replacement or the one-tenth ring carbon atom number of non-replacement be 6～50 aryloxy group and arylthio be expressed as respectively-OY and-SY, Y is from above-mentioned R
1～R
8The replacement or the one-tenth ring carbon atom number of non-replacement be to select in 6～50 the aryl.
R
1～R
8And R
11Replacement or the carbon number of non-replacement be that 2～50 alkoxy carbonyls (carbon number of moieties is 1～49) are expressed as-COOZ, Z is from above-mentioned R
1～R
8The replacement or the carbon number of non-replacement be to select in 1～50 the alkyl.
As R
1～R
8And R
11The replacement silicyl, can enumerate trimethyl silyl, triethylsilyl, t-butyldimethylsilyl, vinyl-dimethyl base silicyl, propyl-dimethyl silicyl, triphenyl silicyl etc.
As R
1～R
8And R
11Halogen atom, can enumerate fluorine, chlorine, bromine, iodine etc.
The barrier layer is also undertaken and is prevented that the 3 heavy attitude excitons that generate in the luminescent layer from spreading the effect of also efficiently injecting electronics to luminescent layer simultaneously to the electric transmission zone.When the electronics injection to luminescent layer descended, because the compound minimizing in the electronics-hole in the luminescent layer, therefore the density of 3 heavy attitude excitons reduced.When the density of 3 heavy attitude excitons reduced, the collision frequency of 3 heavy attitude excitons reduced, and can not efficiently cause the TTF phenomenon.From causing efficiently,, can consider following two kinds as the form in the electric transmission zone that comprises the barrier layer to the viewpoint of the electronics injection of luminescent layer.
(1) the electric transmission zone is made as the stepped construction of two above different materials, between barrier layer and negative electrode, is provided for efficiently obtaining the electron injecting layer of electronics from negative electrode.As the concrete example of electron injecting layer, can enumerate nitogen-contained heterocycle derivant etc.
(2) constitute the electric transmission zone with 1 layer of barrier layer.At this moment, in order to obtain electronics from negative electrode easily, mixing with alkali metal near the cathode interface in the barrier layer is the donor of representative.As donor, can from donor metal, donor metallic compound and donor metal complex, select at least a.
So-called donor metal is meant that work function is the following metal of 3.8eV, preferred as alkali, alkaline-earth metal and rare earth metal, more preferably Cs, Li, Na, Sr, K, Mg, Ca, Ba, Yb, Eu and Ce.
So-called donor metallic compound is meant the compound that contains above-mentioned donor metal, is preferably the compound that contains alkali metal, alkaline-earth metal or rare earth metal, more preferably halogen thing, oxide, carbonate, the borate of these metals.For example be MOx (M is the donor metal, and x is 0.5～1.5), MFx (x is 1～3), M (CO
3) the represented compound of x (x is 0.5～1.5).
So-called donor metal complex is meant the complex compound of above-mentioned donor metal, is preferably the metal-organic complex of alkali metal, alkaline-earth metal or rare earth metal.The represented metal-organic complex of preferred following formula (I).
(in the formula, M is the donor metal; Q is a part, is preferably carboxylic acid derivates, derovatives or quinoline; N is 1～4 integer.)
As the concrete example of donor metal complex, can enumerate the described tungsten waterwheel of TOHKEMY 2005-72012 communique etc.And then the central metal of putting down in writing in the Japanese kokai publication hei 11-345687 communique is that the phthalocyanine compound of alkali metal, alkaline-earth metal etc. also can be used as the donor metal complex and uses.
Above-mentioned donor can be used alone, and also can be used in combination two or more.
Among the present invention, the exciton density at luminescent layer and interface, barrier layer is big.At this moment, probability that the hole is injected in the barrier layer increases, and this is helpless to compound in the luminescent layer.Therefore, as the material that uses in the barrier layer, be preferably the material of oxidation excellent in te pins of durability.
Concrete example as the material of oxidation excellent in te pins of durability, be preferably the hydrocarbon aromatic compound, the compound more than a kind that is preferably the following formula (A) from Japanese Patent Application 2009-090379 specification, put down in writing, (B) especially and (C) selects in the represented polycyclc aromatic compound.
Ra-Ar
101-Rb…(A)
Ra-Ar
101-Ar
102-Rb…(B)
Ra-Ar
101-Ar
102-Ar
103-Rb…(C)
In the formula, Ar
101, Ar
102, Ar
103, Ra and Rb represent to replace or the phenyl ring of non-replacement or from replacing or naphthalene nucleus, replacement or the non-replacement of non-replacement
The benzo [9 of dibenzo phenanthrene ring, replacement or the non-replacement of benzo phenanthrene ring, replacement or the non-replacement of phenanthrene ring, replacement or the non-replacement of fluoranthene ring, replacement or the non-replacement of ring, replacement or non-replacement, 10] benzo of the benzo of phenanthrene ring, replacement or non-replacement [a] benzo [9,10] phenanthrene ring, replacement or non-replacement
The Ppolynuclear aromatic skeleton portion of selecting in the fluorenes ring of the benzo of ring, replacement or non-replacement [b] fluoranthene ring, replacement or non-replacement and replacement or the non-replacement De Pi ring.Wherein, the substituting group of Ra and Rb is not an aryl.Ar
1, Ar
2, Ar
3, Ra and Rb be simultaneously for replacing or the phenyl ring of non-replacement.
In above-mentioned polycyclc aromatic compound, any one among Ra and the Rb or both preferably from replace or the fluoranthene ring of benzo [c] phenanthrene ring of phenanthrene ring, replacement or the non-replacement of non-replacement and replacement or non-replacement select.
The Ppolynuclear aromatic skeleton portion of above-mentioned polycyclc aromatic compound also can have substituting group.
Substituting group as the Ppolynuclear aromatic skeleton portion, for example, can enumerate the alkoxy carbonyl or the carboxyl of aryloxy group, replacement or non-replacement of aralkyl, replacement or non-replacement of aromatic heterocycle, replacement or non-replacement of aromatic hydrocarbyl, replacement or non-replacement of alkoxyl, replacement or non-replacement of cycloalkyl, replacement or non-replacement of thiazolinyl, replacement or non-replacement of alkyl, replacement or non-replacement of amino, nitro, cyano group, replacement or the non-replacement of halogen atom, hydroxyl, replacement or non-replacement.As the preference of aromatic hydrocarbyl, can enumerate naphthalene, phenanthrene, fluorenes,
Fluoranthene and benzo [9,10] phenanthrene.
When the Ppolynuclear aromatic skeleton portion had a plurality of substituting group, these substituting groups can form ring.
The skeleton portion of Ppolynuclear aromatic is preferably any that select from the represented compound in following formula (1)～(4).
In formula (1)～(4), Ar
1～Ar
5The nucleus carbon atom number of expression replacement or non-replacement is 4～16 condensed ring structure.
As the represented compound of formula (1), for example can enumerate replace or the phenanthrene of non-replacement,
Monomer or derivative etc.
As the represented compound of formula (2), for example can enumerate and to replace or the monomer of the acenaphthylene of non-replacement, acenaphthene, fluoranthene or derivative etc.
As the represented compound of formula (3), for example can enumerate and to replace or the monomer of the benzofluoranthrene of non-replacement or derivative etc.
As the represented compound of formula (4), for example can enumerate and to replace or the monomer of the naphthalene of non-replacement or derivative etc.
As naphthalene derivatives, can enumerate the compound of for example following formula (4A).
In the formula (4A), R
1～R
8Represent hydrogen atom respectively independently; Perhaps the nucleus carbon atom number is that aryl, the carbon number of 5～30 substituting group or non-replacement are that alkyl, the carbon number of 1～30 side chain or straight chain is the independent a kind of substituting group in the cycloalkyl of 3～20 replacement or non-replacement, or the substituting group that the multiple combination in them is constituted.
As phenanthrene derivative, can enumerate the compound of for example following formula (5A).
In the formula (5A), R
1～R
10Represent hydrogen atom respectively independently; Perhaps the nucleus carbon atom number is that aryl, the carbon number of 5～30 substituting group or non-replacement are that alkyl, the carbon number of 1～30 side chain or straight chain is the independent a kind of substituting group in the cycloalkyl of 3～20 replacement or non-replacement, or the substituting group that the multiple combination in them is constituted.
As
Derivative can be enumerated the compound of for example following formula (6A).
In the formula (6A), R
1～R
12Represent hydrogen atom respectively independently; Perhaps the nucleus carbon atom number is that aryl, the carbon number of 5～30 substituting group or non-replacement are that alkyl, the carbon number of 1～30 side chain or straight chain is the independent a kind of substituting group in the cycloalkyl of 3～20 replacement or non-replacement, the perhaps substituting group that the multiple combination in them is constituted.
In addition, above-mentioned Ppolynuclear aromatic skeleton portion is preferably the luxuriant and rich with fragrance or derivatives thereof of benzo [c].As benzo [c] phenanthrene derivative, can enumerate the compound of for example following formula (7A).
In the formula (7A), R
1～R
9Represent hydrogen atom respectively independently; Perhaps the nucleus carbon atom number is that aryl, the carbon number of 5～30 substituting group or non-replacement are that alkyl, the carbon number of 1～30 side chain or straight chain is the independent a kind of substituting group in the cycloalkyl of 3～20 replacement or non-replacement, or the substituting group that the multiple combination in them is constituted.
And then above-mentioned Ppolynuclear aromatic skeleton portion is preferably benzo [c]
Or derivatives thereof.As benzo [c]
Derivative can be enumerated the compound of for example following formula (8A).
In the formula (8A), R
1～R
11Represent hydrogen atom respectively independently; Perhaps the nucleus carbon atom number is that aryl, the carbon number of 5～30 substituting group or non-replacement are that alkyl, the carbon number of 1～30 side chain or straight chain is the independent a kind of substituting group in the cycloalkyl of 3～20 replacement or non-replacement, or the substituting group that the multiple combination in them is constituted.
Above-mentioned Ppolynuclear aromatic skeleton portion is preferably the luxuriant and rich with fragrance or derivatives thereof of the represented dibenzo of following formula (9) [c, g].
In addition, above-mentioned Ppolynuclear aromatic skeleton portion is preferably the fluoranthene or derivatives thereof.As the fluoranthene derivative, can enumerate the compound of for example following formula (10A).
In the formula (10A), X
12～X
21The expression hydrogen atom; Halogen atom; The alkyl of straight chain, side chain or ring-type; The alkoxyl of straight chain, side chain or ring-type; The aryl of replacement or non-replacement; Perhaps replace or the heteroaryl of non-replacement.
And then above-mentioned Ppolynuclear aromatic skeleton portion is preferably the luxuriant and rich with fragrance or derivatives thereof of benzo [9,10].As benzo [9,10] phenanthrene derivative, can enumerate the compound of for example following formula (11A).
In the formula (11A), R
1～R
6Represent hydrogen atom respectively independently; Perhaps the nucleus carbon atom number is that aryl, the carbon number of 5～30 replacement or non-replacement are that alkyl, the carbon number of 1～30 side chain or straight chain is the independent a kind of substituting group in the cycloalkyl of 3～20 replacement or non-replacement, or the substituting group that the multiple combination in them is constituted.
Above-mentioned polycyclc aromatic compound can be the represented compound of following formula (12).
In the formula (12), used identical in Ra, Rb and the above-mentioned formula (A)～(C).When Ra, Rb, naphthalene nucleus have one or more substituting groups, substituting group can be that carbon number is that 1～20 alkyl, carbon number are that 1～20 haloalkyl, carbon number are that 5～18 cycloalkyl, carbon number are 3～20 silicyl, cyano group or halogen atom, and the substituting group of the naphthalene nucleus beyond Ra, the Rb can also be that carbon number is 6～22 aryl.
In the formula (12), Ra and Rb are preferably from fluorenes ring, phenanthrene ring, benzo [9,10] phenanthrene ring, benzo phenanthrene ring, dibenzo phenanthrene ring, benzo benzo [9,10] phenanthrene ring, fluoranthene ring, benzo
Ring, benzo [b] fluoranthene Huan are with the group of selecting in the Pi ring.
As barrier material, can use following formula (11), (21) represented nitogen-contained heterocycle derivant.
(in the formula, R
1～R
12In any 12-a one-tenth ring carbon atom number of being respectively hydrogen atom, fluorine atom, replacement or non-replacement be that the one-tenth annular atoms number of 6～30 aryl or replacement or non-replacement is 5～30 heterocyclic radical; R
1～R
12In any a be singly-bound, with L
1Bonding.
L
1For the one-tenth ring carbon atom number of singly-bound, replacement or non-replacement is that the one-tenth annular atoms number of 6～30 b+1 valency hydrocarbon cyclic base or replacement or non-replacement is 5～30 b+1 valency heterocyclic radical.
HAr is the nitrogen heterocycle of replacement or non-replacement.
A and b are respectively 1～4 integer, and at least one among a and the b is 1.)
(in the formula, R
201～R
214In any 14-a be respectively hydrogen atom, fluorine atom, the carbon number of replacement or non-replacement is 1～10 alkyl, the carbon number of replacement or non-replacement is 3～8 cycloalkyl, the carbon number of replacement or non-replacement is 3～30 alkyl silicyl, the one-tenth ring carbon atom number of replacement or non-replacement is 8～30 aryl silicyl, the carbon number of replacement or non-replacement is 1～20 alkoxyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～20 aryloxy group, the one-tenth ring carbon atom number of replacement or non-replacement is 6～30 aryl, perhaps the one-tenth annular atoms number of replacement or non-replacement is 5～30 heterocyclic radical; R
201～R
214In any a be singly-bound, with L
1Bonding.
L
1The one-tenth ring carbon atom number of expression singly-bound, replacement or non-replacement is that the one-tenth annular atoms number of 6～30 b+1 valency hydrocarbon cyclic base or replacement or non-replacement is 5～30 b+1 valency heterocyclic radical.
HAr is the nitrogen heterocycle of replacement or non-replacement.
A and b are respectively 1～4 integer, and at least one among a and the b is 1.)
As the example of the HAr of above-mentioned formula (11), (21), the group of following formula can example be shown.
(in the formula, R
111～R
130Be respectively hydrogen atom or substituting group, R
111～R
130Can with the substituting group of adjacency bonding and form saturated or undersaturated ring each other.
R
111～R
115In any, R
116～R
119In any, R
120～R
122In any, R
123～R
126In any and R
127～R
130In any be singly-bound, with L
1Bonding.)
As barrier material, can use the represented nitogen-contained heterocycle derivant of following formula (31).
(in the formula, R
401～R
416Represent hydrogen atom respectively, fluorine atom, the carbon number of replacement or non-replacement is 1～10 alkyl, the carbon number of replacement or non-replacement is 3～10 cycloalkyl, the carbon number of replacement or non-replacement is 3～30 alkyl silicyl, the one-tenth ring carbon atom number of replacement or non-replacement is 8～30 aryl silicyl, the carbon number of replacement or non-replacement is 1～20 alkoxyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～20 aryloxy group, the alkyl amino of replacement or non-replacement, the arylamino of replacement or non-replacement, the one-tenth ring carbon atom number of replacement or non-replacement is 6～30 aryl, perhaps the one-tenth annular atoms number of replacement or non-replacement is 5～30 heterocyclic radical.R
401～R
410In one and R
411～R
416In 1 be singly-bound, with L
1Bonding.R
411～R
416Can with the substituting group of adjacency bonding and form saturated or undersaturated ring each other.
L
1The one-tenth ring carbon atom number of expression singly-bound, replacement or non-replacement is that the one-tenth annular atoms number of 6～30 c+d valency hydrocarbon cyclic base or replacement or non-replacement is 5～30 c+d valency heterocyclic radical.
C and d represent 1～3 integer respectively.
Wherein, L
1, R
401～R
416It or not the group that contains anthracene.)
And then, as barrier material, can use the material at the triplet barrier structure position that has the electric transmission structure position and comprise the fused-ring aromatic hydrocarbon compound.
The electric transmission structure position for example comprises the ring of selecting more than a kind from following ring.
Triplet barrier structure position is for example selected from following ring.
(in formula (1)～(6), Ar
1～Ar
9Be expressed as the ring carbon atom number and be 4～16 condensed ring structure.)
And then, as barrier material, can use following formula (I), (II) represented phenanthroline derivative.
(in the above-mentioned formula, the group that R is formed by connecting for the alkyl of hydrogen atom, fluorine atom, replacement or non-replacement, cycloalkyl, aryl, heteroaryl, alkoxyl, aryloxy group, alkyl amino, arylamino, alkyl silicyl, aryl silicyl, nitro, cyano group or 2～3 above-mentioned aryl and heteroaryl respectively independently.)
(in the above-mentioned formula, among the R any be as singly-bound and B bonding, the group that remaining R is formed by connecting for the alkyl of hydrogen atom, fluorine atom, replacement or non-replacement, cycloalkyl, aryl, heteroaryl, alkoxyl, aryloxy group, alkyl amino, arylamino, alkyl silicyl, aryl silicyl, nitro, cyano group or 2～3 above-mentioned aryl and heteroaryl respectively independently.M is the integer more than 2.B is a singly-bound; Perhaps as the m valency inferior heteroaryl of m valency arlydene, replacement or the non-replacement of the alkenylene, replacement or the non-replacement that connect m valency alkylidene, replacement or non-replacement base, replacement or non-replacement, 2～4 aryl and the m valency group of heteroaryl be combined into or the m valency group shown in the following formula (b).
Ar
1’-Y-Ar
2’ (b)
(in the formula (b), Ar
1 'With Ar
2 'Can be identical or different, Ar
1 'For replacing or the arlydene or the inferior heteroaryl of (j+1) valency of non-replacement Ar
2 'For replacing or the arlydene or the inferior heteroaryl of (k+1) valency of non-replacement.J and k are respectively the integer more than 1 independently, j+k=m, Ar
1 'And Ar
2 'All the phenanthroline structure with formula (II) combines.Y is O, S or CR '
2, R '
2Independently for replacing or the aryl of alkyl, replacement or the non-replacement of non-replacement, perhaps replace or the heteroaryl of non-replacement R '
2Can become key each other and form saturated or undersaturated ring.))
In above-mentioned phenanthroline derivative, as aryl, can preferably enumerate phenyl, xenyl, ortho-terphenyl base, meta-terphenyl base, para-terpheny base, naphthyl, phenanthryl,
Base, benzo phenanthryl, benzo
Base, benzo anthryl, triphenyl, fluoranthene base, benzofluoranthrene base, fluorenyl etc.As heteroaryl, can preferably enumerate pyridine radicals, pyrimidine radicals, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, naphthyridines base, imidazopyridyl, indyl, indazolyl, phenanthroline base, imidazole radicals, pyrazolyl, pyrrole radicals, furyl, thienyl, oxazolyl, thiazolyl, benzoxazolyl, benzothiazolyl, oxadiazole base, thiadiazolyl group, triazolyl, tetrazole radical, dibenzofuran group, dibenzothiophenes base, carbazyl etc.
As barrier material, can use the represented nitogen-contained heterocycle derivant of following formula.
(in the above-mentioned formula, Ar is the arlydene or the inferior heteroaryl of replacement or non-replacement.X is CR or N respectively independently.Among the R any be as singly-bound and Ar bonding, the group that remaining R is formed by connecting for the alkyl of hydrogen atom, fluorine atom, replacement or non-replacement, cycloalkyl, aryl, heteroaryl, alkoxyl, aryloxy group, alkyl amino, arylamino, alkyl silicyl, aryl silicyl, nitro, cyano group or 2～3 above-mentioned aryl and heteroaryl respectively independently.N is 2 or 3 integer.)
In above-mentioned, as aryl, can preferably enumerate phenyl, xenyl, ortho-terphenyl base, meta-terphenyl base, para-terpheny base, naphthyl, phenanthryl,
Base, benzo phenanthryl, benzo
Base, benzo anthryl, triphenyl, fluoranthene base, benzofluoranthrene base, fluorenyl etc.As heteroaryl, can preferably enumerate pyridine radicals, pyrimidine radicals, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, naphthyridines base, imidazopyridyl, indyl, indazolyl, phenanthroline base, imidazole radicals, pyrazolyl, pyrrole radicals, furyl, thienyl, oxazolyl, thiazolyl, benzoxazolyl, benzothiazolyl, oxadiazole base, thiadiazolyl group, triazolyl, tetrazole radical, dibenzofuran group, dibenzothiophenes base, carbazyl etc.Arlydene is the residue of 2 or 3 valencys of above-mentioned aryl, and inferior heteroaryl is the residue of 2 or 3 valencys of above-mentioned heteroaryl.
As barrier material, can use following formula represented contain the oxygen fused-ring derivatives.
(in the formula, Ar
1Condense the condensed ring radical that forms for having rings ring, more than 4 that are selected from more than 1 in furan nucleus and the pyranoid ring.
HAr is any in the represented nitrogen heterocycle of following formula.
N and m are respectively 1～5 integer.
L is a singly-bound; The one-tenth ring carbon atom number of replacement or non-replacement is 6～30 n+m valency aryl; The one-tenth annular atoms number of replacement or non-replacement is 5～30 n+m valency heterocyclic radical; Perhaps from replacing or the one-tenth ring carbon atom number of non-replacement is that the annular atoms number that becomes of 6～30 aryl and replacement or non-replacement is 2 or 3 n+m valency groups that group is formed by connecting with singly-bound selecting 5～30 the heterocyclic radical.)
(in the formula, R
11, R
12, R
21, R
22, R
31～R
40And R
41～R
46Be hydrogen atom independently respectively, halogen atom, the carbon number of replacement or non-replacement is 1～10 alkyl, replace or the one-tenth ring carbon atom number of non-replacement is that 3～8 cycloalkyl carbon number is 3～30 replacement silicyl cyano group, the carbon number of replacement or non-replacement is 1～20 alkoxyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～20 aryloxy group, the carbon number of replacement or non-replacement is 1～20 alkylthio group, amino, the carbon number of replacement or non-replacement is 1～20 alkyl monosubstituted amino or dialkyl amido, the one-tenth ring carbon atom number of replacement or non-replacement is 6～30 aryl, perhaps the one-tenth annular atoms number of replacement or non-replacement is 5～30 heterocyclic radical.
R
31～R
35In any and R
36～R
40In any be with two pyridine rings of formula (4) singly-bound of bonding each other.
X is N or CR
13, R
13Be hydrogen atom, halogen atom, the carbon number of replacement or non-replacement is 1～10 alkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 3～8 cycloalkyl, carbon number is 3～30 replacement silicyl, cyano group, the carbon number of replacement or non-replacement is 1～20 alkoxyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～20 aryloxy group, the carbon number of replacement or non-replacement is 1～20 alkylthio group, amino, the carbon number of replacement or non-replacement is 1～20 alkyl monosubstituted amino or dialkyl amido, the one-tenth ring carbon atom number of replacement or non-replacement is 6～30 aryl, perhaps the one-tenth annular atoms number of replacement or non-replacement is 5～30 heterocyclic radical.
When there being a plurality of R
13The time, each R
13Can be identical or different.
Y is N or CR
23, R
23Be hydrogen atom, halogen atom, the carbon number of replacement or non-replacement is 1～10 alkyl, the one-tenth ring carbon atom number of replacement or non-replacement is 3～8 cycloalkyl, carbon number is 3～30 replacement silicyl, cyano group, the carbon number of replacement or non-replacement is 1～20 alkoxyl, the one-tenth ring carbon atom number of replacement or non-replacement is 6～20 aryloxy group, the carbon number of replacement or non-replacement is 1～20 alkylthio group, amino, the carbon number of replacement or non-replacement is 1～20 alkyl monosubstituted amino or dialkyl amido, the one-tenth ring carbon atom number of replacement or non-replacement is 6～30 aryl, perhaps the one-tenth annular atoms number of replacement or non-replacement is 5～30 heterocyclic radical.
When there being a plurality of R
23The time, each R
23Can be identical or different.
Z is the bridge joint base, and it is to replace or the alkylidene of non-replacement or the alkenylene of replacement or non-replacement.
R
11～R
13In any, R
21～R
23In any, R
31～R
40In any and R
41～R
46In any be singly-bound with the L bonding.)
As barrier material, can use following carbazole azine based compound and scalariform (ladder-based) based compound.
(1) carbazole azine system
(Cz-)mA
(in the formula, Cz is for replacing or the carbazyl of non-replacement or the azepine carbazyl of replacement or non-replacement.A is that aryl replaces nitrogenous cyclic group, diaryl replaces nitrogenous cyclic group or triaryl replaces nitrogenous cyclic group.M is 1～3 integer.)
Cz-An
(in the formula, Cz is for replacing or the carbazyl of non-replacement or the azepine carbazyl of replacement or non-replacement.A is that aryl replaces nitrogenous cyclic group, diaryl replaces nitrogenous cyclic group or triaryl replaces nitrogenous cyclic group.N is 1～3 integer.)
(2) scalariform system
(in formula (1) and (2), Ar
1, Ar
2And Ar
3Expression replaces or the one-tenth ring carbon atom number of non-replacement is that the one-tenth annular atoms number of 6 aromatic hydrocarbyl or replacement or non-replacement is 6 aromatic heterocycle independently respectively.
Wherein, Ar
1, Ar
2And Ar
3Can have one or more substituting group Y, when a plurality of substituting group, can have nothing in common with each other.
Y represents that carbon number is that the one-tenth ring carbon atom number of 1～20 alkyl, replacement or non-replacement is that 3～20 cycloalkyl, carbon number are that 1～20 alkoxyl, carbon number are that 7～24 aralkyl, silicyl or carbon number are that the one-tenth ring carbon atom number of 3～20 replacement silicyl, replacement or non-replacement is 6～24 aromatic hydrocarbyl or condenses aromatic hydrocarbyl or become the ring carbon atom number and be the aromatic heterocycle of 3～24 replacement or non-replacement or condense aromatic heterocycle.
In formula (1) and (2), X
1, X
2, X
3And X
4Represent oxygen (O), sulphur (S), N-R respectively independently
1Or CR
2R
3
Above-mentioned R
1, R
2And R
3Represent independently that respectively carbon number is that the one-tenth ring carbon atom number of 1～20 alkyl, replacement or non-replacement is that 3～20 cycloalkyl, carbon number are that 7～24 aralkyl, silicyl or carbon number are that the one-tenth ring carbon atom number of 3～20 replacement silicyl, replacement or non-replacement is 6～24 aromatic hydrocarbyl or condense aromatic hydrocarbyl or the one-tenth ring carbon atom number of replacement or non-replacement is 3～24 aromatic heterocycle or condenses aromatic heterocycle.
Wherein, at X
1With X
2Be N-R
1And o, p are 0, and q is under 1 the situation or at X
1And X
3Be N-R
1And p, q are 0, and o is under 1 the situation, R
1At least 1 expression replace or the one-tenth annular atoms number of non-replacement is that 8～24 1 valency condenses aromatic heterocycle.
In formula (1) and (2), o, p and q represent 0 or 1.S represents 1,2,3 or 4, is respectively with L
4As 1 aggressiveness, 2 aggressiveness, 3 aggressiveness, 4 aggressiveness that connect base.R represents 1,2,3 or 4.
In formula (1) and (2), L
2Expression singly-bound, carbon number be the one-tenth ring carbon atom number of 1～20 alkylidene, replacement or non-replacement be 3～20 ring alkylidene, divalent silicyl or carbon number be one-tenth ring carbon atom number that 2～20 divalent replaces silicyl, replacement or non-replacement be the aromatic hydrocarbyl of 6～24 divalent or condense aromatic hydrocarbyl or become the ring carbon atom number be 3～24 replacement or non-replacement divalent aromatic heterocycle or condense aromatic heterocycle.
In the formula (1), L
3Expression singly-bound, carbon number be the one-tenth ring carbon atom number of 1～20 alkylidene, replacement or non-replacement be 3～20 ring alkylidene, divalent silicyl or carbon number be one-tenth ring carbon atom number that 2～20 divalent replaces silicyl, replacement or non-replacement be the aromatic hydrocarbyl of 6～24 divalent or condense aromatic hydrocarbyl or become the ring carbon atom number be 3～24 replacement or non-replacement divalent aromatic heterocycle or condense aromatic heterocycle.
In the formula (2), be 2 o'clock at s, L
4Expression singly-bound, carbon number be the one-tenth ring carbon atom number of 1～20 alkylidene, replacement or non-replacement be 3～20 ring alkylidene, divalent silicyl or carbon number be one-tenth ring carbon atom number that 2～20 divalent replaces silicyl, replacement or non-replacement be the aromatic hydrocarbyl of 6～24 divalent or condense aromatic hydrocarbyl or become the ring carbon atom number be 3～24 replacement or non-replacement divalent aromatic heterocycle or condense aromatic heterocycle.
At s is 3 o'clock, L
4The expression carbon number be the one-tenth ring carbon atom number of 1～20 3 valency saturated hydrocarbyls, replacement or non-replacement be 3～20 3 valency cyclic saturated hydrocarbon bases, 3 valency silicyls or carbon number be one-tenth ring carbon atom number that 1～20 3 valencys replace silicyl, replacement or non-replacement be the aromatic hydrocarbyl of 6～24 3 valencys or condense aromatic hydrocarbyl or become the ring carbon atom number be 3～24 replacement or non-replacement 3 valencys aromatic heterocycle or condense aromatic heterocycle.
At s is 4 o'clock, L
4The expression carbon number be the one-tenth ring carbon atom number of 1～20 4 valency saturated hydrocarbyls, replacement or non-replacement be the one-tenth ring carbon atom number of 3～20 4 valency cyclic saturated hydrocarbon bases, silicon atom, replacement or non-replacement be the aromatic hydrocarbyl of 6～24 4 valencys or condense aromatic hydrocarbyl or become the ring carbon atom number be 3～24 replacement or non-replacement 4 valencys aromatic heterocycle or condense aromatic heterocycle.
In formula (1) and (2), A
1The one-tenth ring carbon atom number of expression hydrogen atom, replacement or non-replacement is that 3～20 cycloalkyl, silicyl or carbon number are that the one-tenth ring carbon atom number of 3～20 replacement silicyl, replacement or non-replacement is 6～24 aromatic hydrocarbyl or condenses aromatic hydrocarbyl or become the ring carbon atom number and be the aromatic heterocycle of 3～24 replacement or non-replacement or condense aromatic heterocycle.
In the formula (1), A
2The one-tenth ring carbon atom number of expression hydrogen atom, replacement or non-replacement is that 3～20 cycloalkyl, silicyl or carbon number are that the one-tenth ring carbon atom number of 3～20 replacement silicyl, replacement or non-replacement is 6～24 aromatic hydrocarbyl or condenses aromatic hydrocarbyl or become the ring carbon atom number and be the aromatic heterocycle of 3～24 replacement or non-replacement or condense aromatic heterocycle.)
Preferably make the X of above-mentioned formula (1) and (2)
1And X
4In a side or X
2And X
3In a side be oxygen atom, and represented compound compound in above-mentioned formula (1) and (2) in molecule, having the dibenzofurans structure.
Further preferably make the X of above-mentioned formula (1) and (2)
1And X
4In a side and X
2And X
3In a side be oxygen atom, and above-mentioned formula (1) and (2) represented compound are the compound with benzofuran and dibenzofurans structure.
The mensuration of＜TTF ratio 〉
Satisfying the relation of regulation by the triplet energies that makes main body, dopant and barrier material, is more than 30% thereby can make with respect to total luminous luminous strength ratio from TTF, can realize the high efficiency that known in the past fluorescent element can't be reached.
Luminous strength ratio from TTF can be measured by transition EL method.So-called transition EL method is to carry out method for measuring to removing the dc voltage luminous decay behavior (transient characteristic) of EL afterwards that element is applied.For the EL luminous intensity, be divided into based on the luminous composition of the initial singlet state exciton that generates in compound with based on the luminous composition of the singlet state exciton that generates via the TTF phenomenon.The life-span of singlet state exciton is the nanosecond order of magnitude, and is very short, so dc voltage is removed back decay rapidly.
On the other hand, the TTF phenomenon is based on the luminous of the singlet state exciton that generates via long triplet exciton of life-span, therefore slowly decay.Like this, exist in time than big-difference, therefore can obtain luminous intensity from TTF based on the luminous of singlet state exciton with based on the luminous of triplet exciton.Specifically can determine by following method.
Transition EL waveform is measured (with reference to Fig. 3) in such a way.To put on EL element from the pulse voltage waveform of voltage impulse generator (PG) output.To apply voltage waveform and input to oscilloscope (OSC).When pulse voltage was put on EL element, EL element produced pulsed illumination.Should luminously input to oscilloscope (OSC) via photoelectron-multiplier-tube (PMT).(PC) receives voltage waveform and pulsed illumination synchronously with personal computer.
And then, by the parsing of transition EL waveform, determine luminous strength ratio in the following manner from TTF.
Draw the ratio equation of the decay behavior of triplet exciton, will be based on the decay behavior modeling of the luminous intensity of TTF phenomenon.For the time decay of the triplet exciton density nT of luminescent layer inside, can use based on the rate of decay α in life-span of triplet exciton with based on the rate of decay γ of the collision of triplet exciton, utilize following ratio equation to represent.
When this differential equation is found the solution approx, obtain following formula.Here, ITTF is the luminous intensity from TTF, and A is a constant.Like this, luminous so long as luminous based on TTF of transition EL, then the subduplicate inverse of its intensity can be shown as near linear.Therefore, with transition EL Wave data and the following approximate expression match of measuring, try to achieve constant A.Remove the luminous intensity 1/A of the moment t=0 of dc voltage this moment
2Be defined as luminous strength ratio from TTF.
The coordinate diagram on Fig. 4 left side is that EL element is applied the dc voltage of regulation, mensuration example when removing voltage subsequently, and the luminous intensity of its expression EL element over time.In the coordinate diagram on Fig. 4 left side, in the moment about 3 * 10
-8During second, remove dc voltage.In addition, the illuminometer in the time of will removing voltage in the coordinate diagram is shown 1.Subsequently up to about 2 * 10
-7After the rapid attenuation of second, slowly attenuance component is displayed.The coordinate diagram on Fig. 4 right side is to remove the voltage moment point as initial point, to removing behind the voltage up to 10
-5As seen the coordinate diagram that the subduplicate inverse of the luminous intensity of second is drawn can be approximately straight line.With straight line portion to the timeorigin overtime, with the value of the intersection point A of the longitudinal axis be 2.41.Like this, the luminous strength ratio from TTF that is obtained by this transition EL waveform is 1/2.41
2=0.17,17% in total luminous intensity is from TTF.
＜the 2 execution mode 〉
Element of the present invention can be made has at least two series element structures that contain the organic layer unit of luminescent layer.Folder is established intermediate layer (being also referred to as intermediate conductive layer, charge generating layer, CGL) between two luminescent layers.The electric transmission zone can be set in each unit.At least 1 luminescent layer is the fluorescence radiation layer, and the unit that contains this luminescent layer satisfies above-mentioned necessary condition.The example of concrete lamination order is as follows.In addition, following luminescent layer can be the duplexer of a plurality of luminescent layers, also can be the organic layer unit that comprises an electric charge barrier layer of aftermentioned the 3rd execution mode.
Anode/fluorescence radiation layer/intermediate layer/fluorescence radiation layer/barrier layer/electron injecting layer/negative electrode
Anode/fluorescence radiation layer/barrier layer/electron injecting layer/intermediate layer/fluorescence radiation layer/negative electrode
Anode/fluorescence radiation layer/barrier layer/intermediate layer/fluorescence radiation layer/barrier layer/electron injecting layer/negative electrode
Anode/phosphorescence luminescent layer/intermediate layer/fluorescence radiation layer/barrier layer/electron injecting layer/negative electrode
Anode/fluorescence radiation layer/barrier layer/electron injecting layer/intermediate layer/phosphorescence luminescent layer/negative electrode
One example of the organic EL of present embodiment shown in Fig. 5.Organic EL 1 possesses anode 10, luminescent layer 22,24 and negative electrode 40 successively, has intermediate layer 60 between luminescent layer 22,24.In electric transmission zone 30, have electron injecting layer 34 and barrier layer 32, barrier layer 32 and luminescent layer 24 adjacency.Luminescent layer 24 is the fluorescence radiation layers that satisfy necessary condition of the present invention.Another luminescent layer can be a fluorescent type, also can be the phosphorescence type.Adjacent at luminescent layer 22 is provided with the barrier layer, can be with luminescent layer 24 as the fluorescence radiation layer that satisfies necessary condition of the present invention.
Need to prove, also can between two luminescent layers 22,24, press from both sides and establish electric transmission zone and/or hole transport zone.In addition, luminescent layer can be more than 3, and the intermediate layer also can be more than two.Be 3 at luminescent layer and between all luminescent layers, can have the intermediate layer when above, also can not have the intermediate layer.
As the intermediate layer material known, can use for example material of middle record such as the 7th, 358, No. 661 specifications of United States Patent (USP), the 10/562nd, No. 124 specification of U.S. Patent application.
＜the 3 execution mode 〉
In the present embodiment, possess anode, a plurality of luminescent layer, electric transmission zone and negative electrode successively, have electric charge barrier layer between any two luminescent layers in a plurality of luminescent layers, the luminescent layer that joins with electric charge barrier layer is the fluorescence radiation layer, and satisfies above-mentioned necessary condition.
Formation as the preferred organic EL of present embodiment, can enumerate as No. 4134280 communique of Japan Patent, U.S. Patent Application Publication 2007/0273270A1 specification, international disclose put down in writing in WO2008/023623A1 number, in the formation that stacks gradually anode, the 1st luminescent layer, electric charge barrier layer, the 2nd luminescent layer and negative electrode, the formation that has the electric transmission zone between the 2nd luminescent layer and negative electrode, described electric transmission zone have the barrier layer and the electron injecting layer of the diffusion that is used to prevent triplet exciton.Here, so-called electric charge barrier layer, be meant by and the luminescent layer of adjacency between the charge carrier that the energy barrier of HOMO energy level, lumo energy adjusts luminescent layer be set inject, be used for adjusting the layer of the carrier balance in luminescent layer injected electrons and hole.
The concrete example of such formation as shown below.
Anode/the 1st luminescent layer/electric charge barrier layer/the 2nd luminescent layer/electric transmission zone/negative electrode
Anode/the 1st luminescent layer/electric charge barrier layer/the 2nd luminescent layer/the 3rd luminescent layer/electric transmission zone/negative electrode
Need to prove, preferably between anode and the 1st luminescent layer, the hole transport zone similarly is set with other execution modes.
One example of the organic EL of present embodiment shown in Fig. 6.The last figure expression element of Fig. 6 constitutes HOMO, the lumo energy with each layer.Figure below is represented the relation of the energy bandgaps on the 3rd luminescent layer and barrier layer.
This organic EL possesses anode, the 1st luminescent layer, the 2nd luminescent layer, the 3rd luminescent layer, electric transmission zone and negative electrode successively, has electric charge barrier layer between the 1st luminescent layer and the 2nd luminescent layer.The electric transmission zone comprises barrier layer and electron injecting layer (not shown).The 3rd luminescent layer is the fluorescence radiation layer that satisfies necessary condition of the present invention.The 1st luminescent layer, the 2nd luminescent layer can be fluorescent types, also can be the phosphorescence types.
The element of present embodiment can be adjusted to white with the illuminant colour of the 1st luminescent layer, the 2nd luminescent layer, the 3rd luminescent layer preferably as white-light luminescent component.In addition, also luminescent layer only can be made as the 1st luminescent layer, the 2nd luminescent layer, be set at white by the illuminant colour of adjusting two luminescent layers.This moment, the 2nd luminescent layer became the fluorescence radiation layer that satisfies necessary condition of the present invention.
Especially be made as the hole transport ability material by main body with the 1st luminescent layer, add the peak wavelength fluorescence radiation dopant bigger than 550nm, the main body of the 2nd luminescent layer (with the 3rd luminescent layer) is made as electron transporting material, add the following fluorescence radiation dopant of peak wavelength 550nm, thereby though be the white-light luminescent component that to realize demonstrating the luminous efficiency higher with the structure that all fluorescent materials constitute than conventional art.
When the hole transmission layer of mentioning especially with the luminescent layer adjacency, cause TTF phenomenon of the present invention for efficient, preferably the bigger situation of triplet energies of hole mobile material when the triplet energies of relatively hole mobile material and main body.
＜the 4 execution mode 〉
In the present embodiment, on substrate, be set up in parallel blue pixel, green pixel, red pixel.In the pixel of these 3 looks, blue pixel has the formation of the 1st execution mode.
One example of the organic EL of present embodiment shown in Fig. 7.
In the last surface-emitting type organic EL 2 shown in this figure, on general substrate 100, form blue pixel B, green pixel G and red pixel R side by side.
Blue pixel B possesses anode 10, hole transport zone 50, blue light-emitting layer 20B, the electric transmission zone 30 that comprises barrier layer and electron injecting layer, negative electrode 40 and protective layer 70 successively from substrate 100.
Green pixel G possesses anode 10, hole transport zone 50, green light emitting layer 20G, the electric transmission zone 30 that comprises barrier layer and electron injecting layer, negative electrode 40 and protective layer 70 successively from substrate 100.
Red pixel R possesses anode 10, hole transport zone 50, red light emitting layer 20R, the electric transmission zone 30 that comprises barrier layer and electron injecting layer, negative electrode 40 and protective layer 70 successively from substrate 100.
Between the anode of each pixel adjacent, form dielectric film 200, keep the insulation between pixel.
In the organic EL 2, the barrier layer is designed in blue pixel B, red pixel R, green pixel G generally.
Though the effect on barrier layer is more remarkable more in the past than the luminous efficiency that obtained in blue fluorescent element, but in green fluorescence element, red fluorescence element, also can obtain triplet energies is strapped in effect same in the luminescent layer, can expect the raising of luminous efficiency.
On the other hand, in the phosphorescence luminescent layer, can obtain triplet exciton is bound by effect in the luminescent layer, prevent the diffusion of triplet energies, help the raising of the luminous efficiency of phosphorescence photism dopant.
The hole transport zone comprises hole transmission layer, hole transmission layer and hole injection layer etc.The hole transport zone can be general, also can be different.Usually, the hole transport zone is set at the formation that is suitable for each illuminant colour.
By the organic layer that luminescent layer 20B, G, R and barrier layer constitute, be not limited to the formation shown in the figure, can suitably change.
Embodiment
The material and the physics value that use in embodiment and the comparative example are as follows.
[hole-injecting material]
[hole mobile material]
[material of main part]
BH
E
T＝1.83eV
Affinity=3eV
[dopant material]
[barrier material]
TB2
E
T＝2.25eV
Affinity=2.9eV
[electronics injection material]
ET
E
T＝1.82eV
Affinity=3eV
The assay method of above-mentioned physics value is as follows.
(1) triplet energies (E
T)
Use commercially available device F-4500 (Hitachi, Ltd's system) to measure.E
TConversion formula as follows.
Conversion formula E
T(eV)=1239.85/ λ
Ph
" λ
Ph" (unit: nm), be meant the longitudinal axis being made as phosphorescence intensity, transverse axis to be made as wavelength when representing phosphorescence spectrum, the ascending curve of the short wavelength side of phosphorescence spectrum is drawn tangent line, the wavelength value of the intersection point of this tangent line and transverse axis.
Each compound is dissolved in (sample 10 μ mol/ liters, EPA (Anaesthetie Ether: isopentane: ethanol=5: 5: 5 (volumetric ratio)), each solvent is the chromatographically pure rank) makes the phosphorimetry sample in the solvent.The phosphorimetry that injects quartz colorimetric utensil is cooled to 77K with sample, phosphorimetry is shone exciting light with sample, Yi Bian change wavelength, Yi Bian measure phosphorescence intensity.In the phosphorescence spectrum longitudinal axis is made as phosphorescence intensity, transverse axis is made as wavelength.
Ascending curve to the short wavelength side of this phosphorescence spectrum draws tangent line, obtains the wavelength value λ of the intersection point of this tangent line and transverse axis
Ph(nm).
Tangent line with respect to the ascending curve of the short wavelength side of phosphorescence spectrum is drawn in the following manner.When on the curve of spectrum when the short wavelength side of phosphorescence spectrum moves that the maximum of minimal wave length side is carried out until the maximum of spectrum, consider the tangent line of the each point on the curve of long wavelength side.This tangent line is along with curve rises (that is, along with the longitudinal axis increases), and slope increases.To be the tangent line of drawing on the point of maximum in the value of this slope as tangent line with respect to the ascending curve of the short wavelength side of this phosphorescence spectrum.
In addition, the maximal point of the peak intensity below 10% with maximum peak intensity of spectrum is not included in the maximum that approaches the minimal wave length side in the maximum of above-mentioned minimal wave length side most, will get the tangent line of drawing on the point of maximum as the tangent line with respect to the ascending curve of the short wavelength side of this phosphorescence spectrum in the value of slope.
(2) affinity (Af)
Measured value by ionization potential (ionization potential) Ip and energy bandgaps Eg is calculated.Calculating formula is as follows.
Af＝Ip-Eg
The absorption edge of the absorption spectrum of energy bandgaps Eg from toluene solution is measured.Particularly, use commercially available visible-ultraviolet specrophotometer measures absorption spectrum, calculate by the decline wavelength of the long wavelength side of this spectrum.
Conversion formula is as follows.
Eg(eV)＝1239.85/λ
ab
To be made as absorbance with the longitudinal axis, transverse axis is made as wavelength and represents that the spectrogram of absorption spectrum is as absorption spectrum.In relating to the above-mentioned conversion formula of energy bandgaps Eg, " λ
Ab" (unit: nm), be meant that the decline curve to the long wavelength side of absorption spectrum draws tangent line, the wavelength value of the intersection point of this tangent line and transverse axis.
Each compound is dissolved in toluene solvant (sample 2 * 10
-5The mol/ liter), be that the mode of 1cm is prepared sample according to optical path length.Measure absorbance while changing wavelength.
With respect to the tangent line of the decline curve of the long wavelength side of absorption spectrum, draw in the following manner.
When on the curve of spectrum from the maximum of absorption spectrum the maximum of long wavelength side when long wavelength's direction moves, consider the tangent line of the each point on the curve.This tangent line is along with curve descends (that is, along with the longitudinal axis reduces), and slope reduces, and increases subsequently, and this phenomenon occurs repeatedly.The tangent line conduct that to draw on the point of long wavelength side (still, getting rid of absorbance is situation 0.1 below) minimalization in the value of slope is with respect to the tangent line of the decline curve of the long wavelength side of this absorption spectrum.
In addition, the value of absorbance is that maximal point below 0.2 is not included in the maximum of above-mentioned long wavelength side.
(3) ionization potential (Ip)
Make the individual course of each layer respectively in the mode of vacuum evaporation on a plurality of ito glass substrates, use the film on the ito glass substrate, (reason is ground gauge (strain) corporate system: AC-3) measure ionization potential to use the photoelectron light-dividing device under atmosphere.Particularly,, measure the amount of electrons that produce based on separation of charge this moment, measure ionization potential thus the material irradiates light.After the photoelectron extraction of square root of emitting, to draw with respect to the energy of irradiates light, the threshold value of photoelectron being emitted energy is as ionization potential (Ip).
On the ito substrate of the ITO that is formed with thickness 130nm, evaporation HI1, HT2, BH, BD-1, TB2, ET successively obtain comprising the element of following formation.Expression thickness (unit: nm) in the parantheses.
ITO(130)/HI1(50)/HT2(45)/BH：BD-1(25：5wt％)/TB2(5)/ET(20)/LiF(1)/Al(80)
Replace BD-1, use the dopant shown in the table 1, in addition obtain element similarly to Example 1.
Comparative example 1～6
Replace BD-1, use the dopant shown in the table 1, do not form the barrier layer, in addition, the thickness of ET is changed to 25nm, obtain element similarly to Example 1.
Evaluation Example 1
Carried out following evaluation for the element that obtains in embodiment 1～6, the comparative example 1～6.The results are shown in table 1.
With the current value is 1mA/cm
2Mode element is applied voltage, measure this moment magnitude of voltage.In addition, use beam split radiance meter (CS-1000: Konica Minolta corporate system) measure EL luminescent spectrum at this moment.By the beam split radiance spectrum that obtains, calculate current efficiency L/J (cd/A), external quantum efficiency EQE (%), peak wavelength λ
p(nm).
Table 1
In the comparative example 1～6, owing to do not form the barrier layer, therefore can not fetter 3 heavy attitude excitons, it is lower than embodiment 1～6 to observe efficient.That is, we can say the effect that demonstrates barrier layer of the present invention among the embodiment 1～6.
Evaluation Example 2
For the element that obtains in embodiment 3 and the comparative example 3, the TTF ratio is measured the result according to following method: observe 25% TTF ratio in the element of embodiment 3, observe 12% TTF ratio in the element of comparative example 3.
Apply from the voltage pulse waveforms (pulse duration: 500 microseconds, frequency: 20Hz, voltage: be equivalent to 0.1～100mA/cm of pulse generator (Agilent corporate system 8114A) output
2Voltage), with the luminous photoelectron-multiplier-tube (the system R928 of creek Song Guangzi company (Hamamatsu Photonics)) that inputs to of EL, make pulse voltage waveform and EL luminous synchronously and input to oscilloscope (Tektronix corporate system 2440), obtain transition EL waveform thus.It is resolved, determine luminous ratio (TTF ratio) from TTF.
Utilizability on the industry
Organic EL of the present invention can use in by the large-scale tv display floater of expectation low consumption electrification, illumination panel etc.
Below embodiments of the present invention and/or embodiment are carried out some detailed descriptions, but those skilled in the art do not break away from substantially in the scope of new enlightenment of the present invention and effect and are easy to these illustrative execution modes and/or embodiment are made numerous variations.Therefore, these numerous variations are also contained in the scope of the present invention.
The content of the document of putting down in writing in this specification all is incorporated herein.
Claims (10)
1. organic electroluminescent device, it possesses anode, luminescent layer, barrier layer, electron injecting layer and negative electrode successively,
Described luminescent layer contains main body and following formula (1) or (2) represented styrylamine derivative,
The 3 heavy attitude energy on described barrier layer are bigger than 3 heavy attitude energy of described main body,
In the formula (1), Ar
1～AR
4Be respectively replacement or the aryl of non-replacement or the heteroaryl of replacement or non-replacement,
Ar
5～Ar
7Be respectively replacement or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement,
L, m and n are respectively 1～3 integer, and p is 0～2 integer,
At l is 2 when above, Ar
5Can be identical or different respectively,
At m is 2 when above, Ar
6Can be identical or different respectively,
At p is more than 1 and n is 2 when above, Ar
7Can be identical or different respectively,
At p is more than 2 and n is 1 o'clock, Ar
7Can be identical or different respectively,
Ar
1～Ar
7Substituting group be the silicyl or the cyano group of halogen atom, alkyl, aryl, heteroaryl, alkoxyl, replacement or non-replacement,
Wherein, at p=0 and (Ar
5)
1During for biphenylene, (Ar
6)
mFor carbon number is a arlydene more than 7, at p=0 and (Ar
6)
mDuring for biphenylene, (Ar
5)
1For carbon number is a arlydene more than 7,
In the formula (2), Ar
8Be replacement or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement,
A
1And A
2Be respectively the heteroaryl or the represented group of following formula (3) of aryl, replacement or the non-replacement of alkyl, replacement or non-replacement,
In the formula (3), Ar
9For replacing or the arlydene of non-replacement or the inferior heteroaryl of replacement or non-replacement B
2For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement, at A
1And A
2When being the group of formula (3), Ar
9And B
2Can be identical or different respectively,
B
1Be replacement or the aryl of non-replacement or the heteroaryl of replacement or non-replacement,
Ar
8～Ar
9, A
1, A
2, B
1And B
2Substituting group be the silicyl or the cyano group of halogen atom, alkyl, aryl, heteroaryl, alkoxyl, replacement or non-replacement.
2. organic electroluminescent device according to claim 1, wherein, in described formula (1) or (2), Ar
1～Ar
4, A
1, A
2, B
1And B
2Has the substituting group that at least one is selected from the silicyl of cyano group, fluorine atom and replacement or non-replacement.
3. organic electroluminescent device according to claim 1 and 2, wherein, in the described formula (1), p is 0, and l is 1, and m is 1.
4. organic electroluminescent device according to claim 1 and 2, wherein, in the described formula (1), p is 1,1 to be 1, and m is 1, and n is 1.
5. organic electroluminescent device according to claim 1 and 2, wherein, in the described formula (1), p is 0, and l is 1, and m is 2.
6. organic electroluminescent device according to claim 1 and 2, wherein, in the described formula (1), p is 0, and l is 2, and m is 2.
7. organic electroluminescent device according to claim 1 and 2, wherein, in the described formula (1), p is 1, and l is 2, and m is 2, and n is 2.
8. organic electroluminescent device according to claim 1, wherein, in the described formula (1), Ar
5～Ar
7In at least one for replacing or the naphthyl of fluorenyl, replacement or the non-replacement of non-replacement or the phenyl of replacement or non-replacement.
9. organic electroluminescent device according to claim 1, wherein, in the described formula (2), Ar
8And Ar
9In at least one for replacing or the naphthyl of fluorenyl, replacement or the non-replacement of non-replacement or the phenyl of replacement or non-replacement.
10. according to each described organic electroluminescent device in the claim 1～8, wherein, in the described formula (1), the structure between two nitrogen is any in the following formula,
In various, the wave at two ends is connected on the nitrogen-atoms.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2010-260607 | 2010-11-22 | ||
| JP2010260607 | 2010-11-22 | ||
| PCT/JP2011/006489 WO2012070227A1 (en) | 2010-11-22 | 2011-11-22 | Organic electroluminescent element |
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|---|---|
| CN103222082A true CN103222082A (en) | 2013-07-24 |
Family
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|---|---|
| US (1) | US20130306957A1 (en) |
| EP (1) | EP2645443A4 (en) |
| JP (1) | JPWO2012070227A1 (en) |
| KR (1) | KR20130135256A (en) |
| CN (1) | CN103222082A (en) |
| TW (1) | TW201226525A (en) |
| WO (1) | WO2012070227A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105684180A (en) * | 2014-10-07 | 2016-06-15 | 出光兴产株式会社 | Organic electroluminescent element and electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6307689B2 (en) | 2012-12-05 | 2018-04-11 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | AMINE DERIVATIVE, ORGANIC LIGHT EMITTING MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME |
| KR102407604B1 (en) | 2013-05-16 | 2022-06-13 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Light-emitting element, light-emitting device, electronic device, and lighting device |
| KR20150130224A (en) | 2014-05-13 | 2015-11-23 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Light-emitting element, light-emitting device, display device, electronic device, and lighting device |
| JP2016100364A (en) | 2014-11-18 | 2016-05-30 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Material for organic electroluminescent element and organic electroluminescent element using the same |
| JP6776309B2 (en) * | 2018-03-30 | 2020-10-28 | キヤノン株式会社 | Organic light emitting element, display device, imaging device and lighting device |
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| JPWO2008156089A1 (en) * | 2007-06-18 | 2010-08-26 | 出光興産株式会社 | Aromatic amine derivative and organic electroluminescence device using the same |
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- 2011-11-22 CN CN2011800563133A patent/CN103222082A/en active Pending
- 2011-11-22 US US13/988,710 patent/US20130306957A1/en not_active Abandoned
- 2011-11-22 WO PCT/JP2011/006489 patent/WO2012070227A1/en active Application Filing
- 2011-11-22 JP JP2012545614A patent/JPWO2012070227A1/en active Pending
- 2011-11-22 TW TW100142681A patent/TW201226525A/en unknown
- 2011-11-22 KR KR1020137013004A patent/KR20130135256A/en not_active Application Discontinuation
- 2011-11-22 EP EP11843161.8A patent/EP2645443A4/en not_active Withdrawn
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| CN105684180A (en) * | 2014-10-07 | 2016-06-15 | 出光兴产株式会社 | Organic electroluminescent element and electronic device |
| CN105684180B (en) * | 2014-10-07 | 2019-06-14 | 出光兴产株式会社 | Organic electroluminescent element and electronic device |
| CN110233206A (en) * | 2014-10-07 | 2019-09-13 | 出光兴产株式会社 | Organic electroluminescent element and electronic device |
| CN110233206B (en) * | 2014-10-07 | 2021-07-30 | 出光兴产株式会社 | Organic electroluminescent element and electronic device |
Also Published As
| Publication number | Publication date |
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| JPWO2012070227A1 (en) | 2014-05-19 |
| EP2645443A1 (en) | 2013-10-02 |
| WO2012070227A1 (en) | 2012-05-31 |
| EP2645443A4 (en) | 2014-04-23 |
| KR20130135256A (en) | 2013-12-10 |
| US20130306957A1 (en) | 2013-11-21 |
| TW201226525A (en) | 2012-07-01 |
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